NiOx (0 < x < 1) modified SrTiO3 (STO) is one of the best studied photocatalyst for overall water splitting under UV light. The established mechanism for this and many other NiOx containing catalysts assumes water oxidation to occur at the early transition metal oxide and water reduction at NiOx. Here we show that NiOx-STO is more likely a three component Ni-STO-NiO catalyst, in which STO absorbs the light, Ni reduces protons, and NiO oxidizes water. This interpretation is based on systematic H2/O2 evolution tests of appropriately varied catalyst compositions using oxidized, chemically and photochemically added nickel and NiO nanoparticle cocatalysts. Surface photovoltage (SPV) measurements reveal that Ni(0) serves as an electron trap (site for water reduction) and that NiO serves as a hole trap (site for water oxidation). Electrochemical measurements show that the overpotential for water oxidation correlates with NiO content, whereas the water reduction overpotential depends on Ni content. Photodeposition experiments with NiCl2 and H2PtCl6 on NiO-STO show that electrons are available on the STO surface, not on the NiO particles. Based on photoelectrochemistry, both NiO and Ni particles suppress the Fermi level in STO, but the effect of this shift on catalytic activity is not clear. Overall, the results suggest a revised role for NiO in NiOx-STO and in many other nickel-containing water splitting systems, including NiOx-La:KTaO3, and many layered perovskites.

Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiOx monolayer film supported on Cu(111), CuTiOx/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiOx is able to stabilize and isolate a single Cu+ site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the LangmuirâHinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu+ site. Upon the formation ofmoreÂ Â» step-edges, the synergy among CuÎ´+ sites, TiOx matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the CuÎ´+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.Â«Â less

The spatially resolved electrical response of rf-sputtered polycrystalline NiOx films composed of 40 nm crystallites was investigated under different relative humidity levels (RH). The topological and electrical properties (surface potential and resistance) were characterized using Kelvin probe force microscopy (KPFM) and conductive scanning probe microscopy at 0%, 50%, and 80% relative humidity with sub 25nm resolution. The surface potential of NiOx decreased by about 180 mV and resistance decreased in a nonlinear fashion by about 2 G when relative humidity was increased from 0% to 80%. The dimensionality of surface features obtained through autocorrelation analysis of topological, surface potential andmoreÂ Â» resistance maps increased linearly with increased relative humidity as water was adsorbed onto the film surface. Spatially resolved surface potential and resistance of the NiOx films were found to be heterogeneous, with distinct features that grew in size from about 60 nm to 175 nm between 0% and 80% RH levels, respectively. Here, we find that the changes in the heterogeneous character of the NiO films are consistent through the topological, surface potential, and resistance measurements, suggesting that the nanoscale surface potential and resistance properties converge with the mesoscale properties as water is adsorbed onto the NiOx film.Â«Â less

One scheme for heating a dense magnetized plasma core, such as in a tokamak, involves launching an ordinary (O) electromagnetic wave at the low density edge. It is converted to a reflected extraordinary (X) electromagnetic wave under certain conditions, and then transformed into an electron Bernstein wave able to reach high density regions inaccessible to most other waves. The O-X mode conversion is important in heating and diagnostic processes in different devices such as tokamaks, stellarators, and some types of pinches. The goal of this study has been to demonstrate that the kinetic particle-in-cell (PIC) scheme is suitable for modeling the O-X conversion process as the first step toward a more complete simulation of O-X-B heating. The O-X process is considered and simulated with a kinetic particle model for parameters of the TJ-II stellarator using the PIC code, XOOPIC. This code is able to model the non-monotonic density and the magnetic profile of the TJ-II stellarator. It can also statistically represent the self-consistent distribution function of the plasma, which has not been possible in previous fluid models. By considering the electric and magnetic components of launched and reflected waves, the O-mode and X-mode waves can be detected, and the O-X conversion can be demonstrated. In this work, the optimum angle for conversion efficiency, as predicted by the previous theory and experimentally confirmed, is used. Via considering the power of the launched O-mode wave and the converted X-mode wave, the efficiency of 63% for O-X conversion for the optimum theoretical launch angle of 47{sup ?} is obtained, which is in good agreement with efficiencies computed via full-wave simulations.

Highlights: {yields} We evaluated the role of miRNAs in ox-LDL induced apoptosis in ECs. {yields} We found 4 up-regulated and 11 down-regulated miRNAs in apoptotic ECs. {yields} Target genes of the dysregulated miRNAs regulate ECs apoptosis and atherosclerosis. {yields} MiR-365 promotes ECs apoptosis via suppressing Bcl-2 expression. {yields} MiR-365 inhibitor alleviates ECs apoptosis induced by ox-LDL. -- Abstract: Endothelial cells (ECs) apoptosis induced by oxidized low-density lipoprotein (ox-LDL) is thought to play a critical role in atherosclerosis. MicroRNAs (miRNAs) are a class of noncoding RNAs that posttranscriptionally regulate the expression of genes involved in diverse cell functions, including differentiation, growth, proliferation, and apoptosis. However, whether miRNAs are associated with ox-LDL induced apoptosis and their effect on ECs is still unknown. Therefore, this study evaluated potential miRNAs and their involvement in ECs apoptosis in response to ox-LDL stimulation. Microarray and qRT-PCR analysis performed on human umbilical vein endothelial cells (HUVECs) exposed to ox-LDL identified 15 differentially expressed (4 up- and 11 down-regulated) miRNAs. Web-based query tools were utilized to predict the target genes of the differentially expressed miRNAs, and the potential target genes were classified into different function categories with the gene ontology (GO) term and KEGG pathway annotation. In particular, bioinformatics analysis suggested that anti-apoptotic protein B-cell CLL/lymphoma 2 (Bcl-2) is a target gene of miR-365, an apoptomir up-regulated by ox-LDL stimulation in HUVECs. We further showed that transfection of miR-365 inhibitor partly restored Bcl-2 expression at both mRNA and protein levels, leading to a reduction of ox-LDL-mediated apoptosis in HUVECs. Taken together, our findings indicate that miRNAs participate in ox-LDL-mediated apoptosis in HUVECs. MiR-365 potentiates ox-LDL-induced ECs apoptosis by regulating the

The crystallization behavior of amorphous TiOxNy (x>>y) thin films was investigated by in-situ transmission electron microscopy. The Johnson-Mehl-Avrami-Kozolog (JMAK) theory is used to determine the Avrami exponent, activation energy, and the phase velocity pre-exponent. Addition of nitrogen inhibits diffusion, increasing the nucleation temperature, while decreasing the growth activation energy. Kinetic variables extracted from individual crystallites are compared to JMAK analysis of the fraction transformed and a change of 6 percent in the activation energy gives agreement between the methods. From diffraction patterns and index of refraction the crystallized phase was found to be predominantly anatase.

The Ag-CuOx system is of interest to be used to be used as an air braze filler metal for joining high temperature electrochemical devices. Previous work has shown that the melting temperatures can be increased by adding palladium to Ag-CuOx and it is expected that this may aid high temperature stability. This work compares the room temperature bend strength of joints made between yttria-stabilized zirconia (YSZ) air brazed using Ag-CuOx without palladium and with 5 and 15mol% palladium additions. It has been found that in general palladium decreases joint strength, especially in low copper oxide compositions filler metals. At high copper oxide contents, brittle fracture through both copper oxide rich phases and the YSZ limits joint strength.

REBa2Cu3Ox superconductor tapes with moderate levels of dopants have been optimized for high critical current density in low magnetic fields at 77 K, but they do not exhibit exemplary performance in conditions of interest for practical applications, i.e., temperatures less than 50 K and fields of 2â30 T. Heavy doping of REBCO tapes has been avoided by researchers thus far due to deterioration in properties. Here, we report achievement of critical current densities (Jc) above 20 MA/cm2 at 30 K, 3 T in heavily doped (25 mol. % Zr-added) (Gd,Y)Ba2Cu3Ox superconductor tapes, which is more than three times higher thanmoreÂ Â» the Jc typically obtained in moderately doped tapes. Pinning force levels above 1000 GN/m3 have also been attained at 20 K. A composition map of lift factor in Jc (ratio of Jc at 30 K, 3 T to the Jc at 77 K, 0 T) has been developed which reveals the optimum film composition to obtain lift factors above six, which is thrice the typical value. A highly c-axis aligned BaZrO3 (BZO) nanocolumn defect density of nearly 7 Ã 1011 cmâ2 as well as 2â3nm sized particles rich in Cu and Zr have been found in the high Jc films.Â«Â less

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of CâH bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100â120 Â°C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 Â°C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140â160 Â°C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganesemoreÂ Â» doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of CâH bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.Â«Â less

This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFeâFeOx nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeOx within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeOx and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, themoreÂ Â» intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFeâFeOx/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.Â«Â less

The reaction of Î³-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the Î³-Al2O3 surface, functionalizing the surface with âmildâ BrÃ¸nsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we used strontium cobaltites (SrCoOx) epitaxially grown by pulsed laser epitaxy (PLE) as a model system to study the oxidation-driven evolution of the structure, electronic, and magnetic properties. We grew coherently strained SrCoO2.5thin films and performed post-annealing at various temperatures for topotacticmoreÂ Â» conversion into the perovskite phase (SrCoO3-Î´). We clearly observed significant changes in electronic transport, magnetism, and microstructure near the critical temperature for the topotactic transformation from the brownmillerite to the perovskite phase. Furthermore, the overall crystallinity was well maintained without much structural degradation, indicating that topotactic phase control can be a useful tool to control the physical properties repeatedly via redox reactions.Â«Â less

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoOx/MoS2 coreâshell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H2 evolution. The 1D nanowires exhibit significant improvement in H2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS2 layers in the outer shell, leadingmoreÂ Â» to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).Â«Â less

Results from studies on exclusive production of electron-position pair, di-photon, and dijet production at CDF in proton-antiproton collisions at the Fermilab Tevatron are presented. THe first observation and cross section measurements of exclusive e{sup +}e{sup -} and di-jet production in hadron-hadron collisions are emphasized.

In this study, tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react withmoreÂ Â» the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of â0.20 V (RHE), lower than that for the latter (â0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.Â«Â less

Semi-inclusive deep inelastic scattering (SIDIS) has been used extensively in recent years as an important testing ground for QCD. Studies so far have concentrated on better determination of parton distribution functions, distinguishing between the quark and antiquark contributions, and understanding the fragmentation of quarks into hadrons. Hadron pair (di-hadron) SIDIS provides information on the nucleon structure and hadronization dynamics that complement single hadron SIDIS. Di-hadrons allow the study of low- and high-twist distribution functions and Dihadron Fragmentation Functions (DiFF). Together with the twist-2 PDFs ( f1, g1, h1), the Higher Twist (HT) e and hL functions are very interesting because they offer insights into the physics of the largely unexplored quark-gluon correlations, which provide access into the dynamics inside hadrons. The CLAS spectrometer, installed in Hall-B at Jefferson Lab, has collected data using the CEBAF 6 GeV longitudinally polarized electron beam on longitudinally polarized solid NH3 targets. Preliminary results on di-hadron beam-, target- and double-spin asymmetries will be presented.

Infrared spectroscopy was used to study the defect spectrum of Cz-Si samples following fast neutron irradiation. We mainly focus on the band at 533 cm{sup ?1}, which disappears from the spectra at ?170 °C, exhibiting similar thermal stability with the Si-P6 electron paramagnetic resonance (EPR) spectrum previously correlated with the di-interstitial defect. The suggested structural model of this defect comprises of two self-interstitial atoms located symmetrically around a lattice site Si atom. The band anneals out following a first-order kinetics with an activation energy of 0.88 ± 0.3 eV. This value does not deviate considerably from previously quoted experimental and theoretical values for the di-interstitial defect. The present results indicate that the 533 cm{sup ?1} IR band originates from the same structure as that of the Si-P6 EPR spectrum.

Basic ReseaRch DiRections for User Science at the National Ignition Facility Report on the National Nuclear Security Administration - Office of Science Workshop on Basic Research Directions on User Science at the National Ignition Facility BASIC RESEARCH DIRECTIONS FOR USER SCIENCE AT THE NATIONAL IGNITION FACILITY Report on the National Nuclear Security Administration (NNSA) - Office of Science (SC) Workshop on Basic Research Directions on User Science at the National Ignition Facility Chairs:

Capture and recycling of COâ into valuable chemicals such as alcohols could help mitigate its emissions into the atmosphere. Due to its inert nature, the activation of COâ is a critical step in improving the overall reaction kinetics during its chemical conversion. Although pure gold is an inert noble metal and cannot catalyze hydrogenation reactions, it can be activated when deposited as nanoparticles on the appropriate oxide support. In this combined experimental and theoretical study, it is shown that an electronic polarization at the metalâoxide interface of Au nanoparticles anchored and stabilized on a CeOx/TiOâ substrate generates active centers formoreÂ Â» COâ adsorption and its low pressure hydrogenation, leading to a higher selectivity toward methanol. In conclusion, this study illustrates the importance of localized electronic properties and structure in catalysis for achieving higher alcohol selectivity from COâ hydrogenation.Â«Â less

Nicholas DiLucia Computer engineer utilizes skills from NETL to update lab website Nicholas DiLucia Nicholas DiLucia returned to the National Energy and Technology Laboratory for the fourth year in a row to engage in website development. His previous internship experiences at the lab helped him succeed in courses at the Univ. of Pittsburgh, where he graduated in April 2012. When Nicholas DiLucia graduated from the Univ. of Pittsburgh in April 2012, he was excited to have a place to go to develop

This paper investigates the effects of high dose rate ionizing radiation and total ionizing dose (TID) on tantalum oxide (TaOx) memristors. Transient data were obtained during the pulsed exposures for dose rates ranging from approximately 5.0 Ã107 rad(Si)/s to 4.7 Ã108 rad(Si)/s and for pulse widths ranging from 50 ns to 50 Î¼s. The cumulative dose in these tests did not appear to impact the observed dose rate response. Static dose rate upset tests were also performed at a dose rate of ~3.0 Ã108 rad(Si)/s. This is the first dose rate study on any type of memristive memory technology. InmoreÂ Â» addition to assessing the tolerance of TaOx memristors to high dose rate ionizing radiation, we also evaluated their susceptibility to TID. The data indicate that it is possible for the devices to switch from a high resistance off-state to a low resistance on-state in both dose rate and TID environments. The observed radiation-induced switching is dependent on the irradiation conditions and bias configuration. Furthermore, the dose rate or ionizing dose level at which a device switches resistance states varies from device to device; the enhanced susceptibility observed in some devices is still under investigation. As a result, numerical simulations are used to qualitatively capture the observed transient radiation response and provide insight into the physics of the induced current/voltages.Â«Â less

There is a need for software that allows a tour guide to present different tracks of slides and then return to the default slide show automatically upon completion. A mobile solution is needed for trade shows. DiTour is an iPad/iPhone app that pulls presentation content from a website, stores it on the device and presents it on a connected display. A tour guide can select a track to present and it will automatically return tomoreÂ Â» the default track after a timeout. It offers a mobile solution which is ideal for trade shows.Â«Â less

Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeOxTiO? catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeOx and TiO?. In these materials the interfaces between CeOx-TiO? have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis and HR-STEM/STEM-EELS, to unravelmore »the local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeOx-TiO? interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeOx loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiO? support. The electronic structures of these catalysts indicate that the interaction between TiO? and CeO? is closely related to the local morphology of nanostructured CeO?. Ce³? cations were detected at the surface of CeO? and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of H?O using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeOx-TiO? catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the interface were critical for the

MgAlOx mixed oxides were employed as supports for potassium-based lean NOx traps (LNTs) targeted for high temperature applications. Effects of support compositions, K/Pt loadings, thermal aging and catalyst regeneration on NOx storage capacity were systematically investigated. The catalysts were characterized by XRD, NOx-TPD, TEM, STEM-HAADF and in-situ XAFS. The results indicate that MgAlOx mixed oxides have significant advantages over conventional gamma-Al2O3-supports for LNT catalysts, in terms of high temperature NOx trapping capacity and thermal stability. First, as a basic support, MgAlOx stabilizes stored nitrates (in the form of KNO3) to much higher temperatures than mildly acidic gamma-Al2O3. Second, MgAlOx minimizes Pt sintering during thermal aging, which is not possible for gamma-Al2O3 supports. Notably, combined XRD, in-situ XAFS and STEM-HAADF results indicate that Pt species in the thermally aged Pt/MgAlOx samples are finely dispersed in the oxide matrix as isolated atoms. This strong metal-support interaction stabilizes Pt and minimizes the extent of sintering. However, such strong interactions result in Pt oxidation via coordination with the support so that NO oxidation activity can be adversely affected after aging which, in turn, decreases NOx trapping ability for these catalysts. Interestingly, a high-temperature reduction treatment regenerates essentially full NOx trapping performance. In fact, regenerated Pt/K/MgAlOx catalyst exhibits much better NOx trapping performance than fresh Pt/K/Al2O3 LNTs over the entire temperature range investigated here. In addition to thermal aging, Pt/K loading effects were systemically studied over the fresh samples. The results indicate that NOx trapping is kinetically limited at low temperatures, while thermodynamically limited at high temperatures. A simple conceptual model was developed to explain the Pt and K loading effects on NOx storage. An optimized K loading, which allows balancing between the

A self-assembled GeOx/reduced graphene oxide (GeOx/RGO) composite, where GeOx nanoparticles were grown directly on reduced graphene oxide sheets, was synthesized via a facile one-step reduction approach and studied by X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, electron energy loss spectroscopy elemental mapping, and other techniques. Electrochemical evaluation indicates that incorporation of reduced graphene oxide enhances both the rate capability and reversible capacity of GeOx, with the latter being due to the RGO enabling reversible utilization of Li2O. The composite delivers a high reversible capacity of 1600 mAhg-1 at a current density of 100 mAg-1, and still maintains a capacity of 410 mAhg-1 at a high current density of 20 Ag-1. Owing to the flexible reduced graphene oxide sheets enwrapping the GeOx particles, the cycling stability of the composite was also improved significantly. To further demonstrate its feasibility in practical applications, the synthesized GeOx/RGO composite anode was successfully paired with a high voltage LiNi0.5Mn1.5O4 cathode to form a full cell, which showed good cycling and rate performance.

Understanding safe operating limits of composite superconducting wires is important for the design of superconducting magnets. Here we report measurements of quench-induced critical current density Jc degradation in commercial Ag/Bi2Sr2CaCu2Ox (Bi-2212) round wires using heater-induced quenches at 4.2 K in self magnetic field that reveal a general degradation behavior. Jc degradation strongly depends on the local hot spot temperature Tmax, and is nearly independent of operating current, the temperature gradient along the conductor dTmax/dx, and the temperature rising rate dTmax/dt. Both Jc and n value (where n is an index of the sharpness of the superconductor-to-normal transition) exhibit small butmoreÂ Â» irreversible degradation when Tmax exceeds 400-450 K, and large degradation occurs when Tmax exceeds 550 K. This behavior was consistently found for a series of Bi-2212 wires with widely variable wire architectures and porosity levels in the Bi-2212 filaments, including a wire processed using a standard partial melt processing and in which Bi-2212 filaments are porous, an overpressure processed wire in which Bi-2212 filaments are nearly porosity-free and that has a Jc(4.2 K, self field) exceeding 8000 A/mm2, and a wire that has nearly no filament to filament bridges after reaction. Microstructural observations of degraded wires reveal cracks in the Bi-2212 filaments perpendicular to the wire axis, indicating that the quench-induced Ic degradation is primarily driven by strain. These results further suggest that the quench degradation temperature limit depends on the strain state of Bi-2212 filaments and this dependence shall be carefully considered when engineering a high-field Bi-2212 magnet.Â«Â less

We report the comprehensive study of the crystal structure of (Ga1âxZnx)(N1âxOx) solid solution nanoparticles by means of neutron and synchrotron x-ray scattering. In our study we used four different types of (Ga1âxZnx)(N1âxOx) nanoparticles, with diameters of 10â27 nm and x = 0.075â0.51, which show the narrow energy-band gaps from 2.21 to 2.61 eV. The Rietveld analysis of the neutron diffraction data revealed that the average crystal structure is the hexagonal wurtzite (space group P63mc), in agreement with previous reports on similar bulk materials. The pair-distribution function (PDF) analysis of the same data found that the local structure is more disorderedmoreÂ Â» than the average one. It is best described by the model with a lower symmetry space group P1, where atoms are quasirandomly distorted from their nominal positions in the hexagonal wurtzite lattice.Â«Â less

The total ionizing dose (TID) effect of gamma-ray (Î³-ray) irradiation on HfOx based resistive random access memory was investigated by electrical and material characterizations. The memory states can sustain TID level â¼5.2 Mrad (HfO{sub 2}) without significant change in the functionality or the switching characteristics under pulse cycling. However, the stability of the filament is weakened after irradiation as memory states are more vulnerable to flipping under the electrical stress. X-ray photoelectron spectroscopy was performed to ascertain the physical mechanism of the stability degradation, which is attributed to the Hf-O bond breaking by the high-energy Î³-ray exposure.

Pulsing 15N18O onto an annealed 1% Mn16Ox/Ce16O2 catalyst resulted in very fast oxygen isotope exchange and 15N2 formation at 295 K. In the 1st 15N18O pulse, due to the presence of large number of surface oxygen defects, extensive 15N218O and 15N2 formations were observed. In subsequent pulses oxygen isotope exchange dominated as a result of highly labile oxygen in the oxide. We gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy/Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOEs Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

A new visible-light-response photocatalyst Sm{sub 2}InTaO{sub 7} with 4f-d{sup 10}-d{sup 0} configuration crystallized in a cubic system with the space group Fd3m was synthesized by a solid-state reaction method. NiOx-loaded Sm{sub 2}InTaO{sub 7} showed high photocatalytic activities for H{sub 2} evolution from pure water under visible light irradiation (lambda>400 nm). Changes in the photocatalytic activity with the calcination temperature of Sm{sub 2}InTaO{sub 7} and the amount of NiOx loaded indicated that the combination of highly crystallized Sm{sub 2}InTaO{sub 7} and a high dispersion of NiOx particles led to high photocatalytic activity. The high photocatalytic performance of NiOx-loaded Sm{sub 2}InTaO{sub 7} supported the existing view that the photocatalytic activity correlated with the lattice distortion. Density functional theory calculation indicated that strong dispersion from the hybridized In 5s 5p orbitals at the bottom of the conduction band was responsible for the high activity of photocatalyst Sm{sub 2}InTaO{sub 7}. - Graphical abstract: A new visible-light-response photocatalyst Sm{sub 2}InTaO{sub 7} with 4f-d{sup 10}-d{sup 0} configuration was developed. DFT calculation indicated that strong dispersion from the hybridized In 5s 5p orbitals was responsible for the high photocatalytic activity.

This thesis consists of two separate parts. The first part addresses the synthesis and study of conjugated polymers containing di- or triphenylamine. Two types of polymers: linear polymers and dendrimers, were synthesized. The polymers were characterized by NMR, IR, UV, GPC, TGA and DSC. Electronic and optical properties of the polymers were studied through the conductivity measurements and excitation- emission spectra. the second part of this thesis deals with a reaction of electron-rich acetylenes with TCNE. The discovery of the reaction from charge transfer complex studies and the investigation of this reaction on various electron-rich acetylenes are presented.

g3t4 6 dI UNIVERSITY OF NEV\DA SYSTEM tw ?r@ D O E / D P / O 1 2 6 3 - 2 0 L , n z l t P ' " WATER RESOURCES CENTER itf.l This report was prepared as an aecount of work sponsore$ by the United States Government. Neither the United States nor the United States Department of Energy, nor any of their employees, mal assumes any legal liability or responsib usefulness of any informationr apparatus' I that its use would not infringe privately speeifie eommereial produetr proeesst ufacturen, or

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO2(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeOx/TiO2(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce3+ oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO2(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H2O + CO ? H2 + CO2) or for the oxidation of carbon monoxide (2CO + O2 ? 2CO2). The enhanced stability of the Ce3+ state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

It is required that Di-2-ethylhexyl Sebacate oil, also commonly known as Dioctyl Sebacate oil, be thoroughly removed from certain metals, in this case stainless steel parts with narrow, enclosed spaces. Dioctyl Sebacate oil is a synthetic oil with a low compressibility. As such, it is ideally used for high pressure calibrations. The current method to remove the Dioctyl Sebacate from stainless steel parts with narrow, enclosed spaces is a labor-intensive, multi-step process, including a detergent clean, a deionized (DI) water rinse, and several solvent rinses, to achieve a nonvolatile residue of0.04 mg per 50 mL rinse effluent. This study was undertaken to determine a superior detergent/solvent cleaning method for the oil to reduce cleaning time and/or the amount of detergent/solvent used. It was determined that while some detergent clean the oil off the metal better than the current procedure, using only solvents obtained the best result. In addition, it can be inferred, based on elevated temperature test results, that raising the temperature of the oil-contaminated stainless steel parts to approximately 50%C2%B0C will provide for improved cleaning efficacy.

Nano-sized La{sub 0.4}Sr{sub 0.6}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (LSCF) perovskite samples (prepared by a conventional acetate route and a novel acetate synthesis with HMTA additives), were tested simulating a red-ox cycle. The crystallography was studied by X-ray Powder Diffraction (XPD) and the changes in the oxidation state of the perovskite B-site were evaluated by synchrotron X-ray Absorption Near Edge Spectroscopy (XANES). After a reducing treatment, LSFC particles show the appearance of a new phase that coexists with the original one. The structural change is accompanied by a Co and Fe formal oxidation states decrease, although Fe remains always closer to 4+ and Co closer to 3+. The treatment produces a B-site valence average reduction from 3.52+ to 3.26+ and the formation of oxygen vacancies. A re-oxidation treatment under O{sub 2} rich atmosphere at 800 Degree-Sign C for 10 h shows that the change is reversible and independent of the two chemical methods used to synthesize the LSCF nano-particles. - Graphical abstract: XANES and XPD measurements in nanostructured LSCF before (black) and after (red/green) a red/ox cycle. Highlights: Black-Right-Pointing-Pointer Red-ox treatments in LSCF nano-particles cause a reversible reaction. Black-Right-Pointing-Pointer XPD analyses show that a new 'reduced' phase coexist with the oxidize one. Black-Right-Pointing-Pointer The B-site formal oxidation state decreases and the {delta} increases upon reduction. Black-Right-Pointing-Pointer Fe remains in a higher valence (closer to 4+) than Co (close to 3+). Black-Right-Pointing-Pointer The behavior seems to be independent of the synthesis method used.

The role of the interface between a metal and oxide (CeOxâCu and ZnOâCu) is critical to the production of methanol through the hydrogenation of CO2 (CO2 + 3H2 â CH3OH + H2O). The deposition of nanoparticles of CeOx or ZnO on Cu(111), Î¸oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeOx/Cu(111). The apparent activation energy for the CO2 â CH3OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeOx/Cu(111). The surface chemistry of the highlymoreÂ Â» active CeOxâCu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOOâ) and carboxylates (CO2Î´â) during the reaction. Our results show an active state of the catalyst rich in Ce3+ sites which stabilize a CO2Î´â species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metalâoxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.Â«Â less

The thrust of this research was to identify and understand current limiting mechanisms (CLMs) that limit the current carrying capacity of (Bi,Pb)2Sr2Ca2Cu3Ox (2223) in Ag-sheathed wire. Our program concentrated on developing new methods to identify CLMs at the micrometer scale and new processing techniques to eliminate CLMs. All of the DOE Superconductivity Partnership Initiative (SPI) programs are using 2223 wire, so increasing the critical current density (Jc) in the wire can improve the technical performance of the demonstration projects, and at the same time it can decrease the cost of the wire. The important cost metric for superconducting wire is $/kAïm, so increasing Jc, which is in the denominator, decreases the wire cost. The obvious CLMs were micrometer size obstacles in the 2223 ceramic that block current flow, including: misaligned grains, cracks, pores, and nonsuperconducting phases. Pores and cracks - regions where there is no superconductor or the grains are not physically connected to one another ? cannot carry supercurrent, so they were the first CLMs we tried to eliminate with improved processing. Prior to the contract, we had started investigating overpressure (OP) processing with Williams at ORNL to heal cracks and remove pores. OP processing, which is a variant of hot isostatic pressing (HIP), uses an Ar/O2 gas mixture to apply a high pressure (up to 200 atm) to compress the sample and to set the oxygen partial pressure (pO2) to form 2223. Williams had a static pressure system we used to demonstrate that OP processing healed cracks and densified the wire, but the static system limited the processing parameters we could investigate. We proposed building a new gas-flow OP system to expand the experimental capabilities and to investigate new processing routes using the gas-flow OP system. Using the gas-flow OP system, we established new world records in 2003 for Jc and Ic. These records were finally matched by Sumitomo Electric Company in early

The lighter mass eigenstate ($\\widetilde{t}_1$) of the two top squarks, the scalar superpartners of the top quark, is extremely difficult to discover if it is almost degenerate with the lightest neutralino ($\\widetilde{\\chi}_1^0$), the lightest and stable supersymmetric particle in the R-parity conserving supersymmetry. The current experimental bound on $\\widetilde{t}_1$ mass in this scenario stands only around 200 GeV. For such a light $\\widetilde{t}_1$, the heavier top squark ($\\widetilde{t}_2$) can also be around the TeV scale. Moreover, the high value of the higgs ($h$) mass prefers the left and right handed top squarks to be highly mixed allowing the possibility of a considerable branching ratio for $\\widetilde{t}_2 \\to \\widetilde{t}_1 h$ and $\\widetilde{t}_2 \\to \\widetilde{t}_1 Z$. In this paper, we explore the above possibility together with the pair production of $\\widetilde{t}_2$ $\\widetilde{t}_2^*$ giving rise to the spectacular di-boson + missing transverse energy final state. For an approximately 1 TeV $\\widetilde{t}_2$ and a few hundred GeV $\\widetilde{t}_1$ the final state particles can be moderately boosted which encourages us to propose a novel search strategy employing the jet substructure technique to tag the boosted $h$ and $Z$. The reconstruction of the $h$ and $Z$ momenta also allows us to construct the stransverse mass $M_{T2}$ providing an additional efficient handle to fight the backgrounds. We show that a 4--5$\\sigma$ signal can be observed at the 14 TeV LHC for $\\sim$ 1 TeV $\\widetilde{t}_2$ with 100 fb$^{-1}$ integrated luminosity.

The potentiality of direct injection (DI) diesel engines for passenger cars has been examined by comparing the characteristics of fuel consumption, exhaust emissions and noise levels between a turbocharged DI diesel engine and a turbocharged IDI diesel engine with the same displacement, 4 cylinders and 2 liters. It was observed that improved fuel consumption was obtained as the engine load increased, namely, 10 - 15% in the higher load range and 5 - 10% in the partial load range. In comparison to the IDI engine, the exhaust emissions of the DI engine tended to contain two or three times higher NOx and HC, and also about 30% higher particulates. Further, the noise levels of the DI engine were approximately 2 - 4 db (a) higher than those of the IDI engine. It was suggested from these results that in those countries which have stringent emission and noise regulations several years would be required to introduce small, high speed DI diesel engines for passenger cars to meet with these regulations.

A method of dissolving metal oxides using a mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

Pseudomonas aeruginosa is an opportunistic human pathogen that secretes the exopolysaccharide alginate during infection of the respiratory tract of individuals afflicted with cystic fibrosis and chronic obstructive pulmonary disease. Among the proteins required for alginate production, Alg44 has been identified as an inner membrane protein whose bis-(3',5')-cyclic dimeric guanosine monophosphate (c-di-GMP) binding activity post-translationally regulates alginate secretion. In this study, we report the 1.8 Ã crystal structure of the cytoplasmic region of Alg44 in complex with dimeric self-intercalated c-di-GMP and characterize its dinucleotide-binding site using mutational analysis. The structure shows that the c-di-GMP binding region of Alg44 adopts a PilZmoreÂ Â» domain fold with a dimerization mode not previously observed for this family of proteins. Moreover, calorimetric binding analysis of residues in the c-di-GMP binding site demonstrate that mutation of Arg-17 and Arg-95 alters the binding stoichiometry between c-di-GMP and Alg44 from 2:1 to 1:1. Introduction of these mutant alleles on the P. aeruginosa chromosome show that the residues required for binding of dimeric c-di-GMP in vitro are also required for efficient alginate production in vivo. Our results suggest that the dimeric form of c-di-GMP represents the biologically active signaling molecule needed for the secretion of an important virulence factor produced by P. aeruginosa.Â«Â less

Pseudomonas aeruginosa is an opportunistic human pathogen that secretes the exopolysaccharide alginate during infection of the respiratory tract of individuals afflicted with cystic fibrosis and chronic obstructive pulmonary disease. Among the proteins required for alginate production, Alg44 has been identified as an inner membrane protein whose bis-(3',5')-cyclic dimeric guanosine monophosphate (c-di-GMP) binding activity post-translationally regulates alginate secretion. In this study, we report the 1.8 Ã crystal structure of the cytoplasmic region of Alg44 in complex with dimeric self-intercalated c-di-GMP and characterize its dinucleotide-binding site using mutational analysis. The structure shows that the c-di-GMP binding region of Alg44 adopts a PilZ domain fold with a dimerization mode not previously observed for this family of proteins. Moreover, calorimetric binding analysis of residues in the c-di-GMP binding site demonstrate that mutation of Arg-17 and Arg-95 alters the binding stoichiometry between c-di-GMP and Alg44 from 2:1 to 1:1. Introduction of these mutant alleles on the P. aeruginosa chromosome show that the residues required for binding of dimeric c-di-GMP in vitro are also required for efficient alginate production in vivo. Our results suggest that the dimeric form of c-di-GMP represents the biologically active signaling molecule needed for the secretion of an important virulence factor produced by P. aeruginosa.

Belgium on the 2014 Nuclear Security Summit | National Nuclear Security Administration | (NNSA) Joint Statement by President Obama and Prime Minister Elio Di Rupo of Belgium on the 2014 Nuclear Security Summit March 24, 2014 See a fact sheet here. The White House Office of the Press Secretary Belgium and the United States of America are pleased to announce that they have jointly completed the removal of a significant amount of excess highly enriched uranium (HEU) and separated plutonium from

This paper describes a feasibility test program on a 2 liter, 4 cylinder DI/TCI passenger car engine operated on the new alternative fuel Dimethyl Ether (DME) with the aim of demonstrating its potential of meeting ULEV (ultra low emission vehicle) emissions (0.2 g/mi NOx in the FTP 75 test cycle) when installed in a full size passenger car. Special attention is drawn to the fuel injection equipment (FIE) as well as combustion system requirements towards the reduction of NOx and combustion noise while keeping energetic fuel consumption at the level of he baseline DI/TCI diesel engine. FIE and combustion system parameters were optimized on the steady state dynamometer by variation of a number of parameters, such as rate of injection, number of nozzle holes, compression ratio, piston bowl shape and exhaust gas recirculation. The paper presents engine test results achieved with DME under various operating conditions and compares these results to those achieved with the diesel version of the same engine.The FTP 75 cycle results were projected from steady state engine maps using a vehicle simulation program taking into account vehicle data and road resistance data of a given vehicle.The cycle results are also compared to actual chassis dynamometer results achieved with the diesel version of the same engine installed in the same vehicle.the passenger car DI/TCI engine adapted for and operated on DME shows very promising results with respect to meeting ULEV NOx emissions without any soot emissions and without the need for a DENOX catalyst. DME fuel consumption on energy basis can be kept very close to the DI diesel value. An oxidation catalyst will be necessary to meet the stringent CO and HC ULEV emission limits.

We study the azimuthal asymmetry of back-to-back di-jet production in unpolarized hadron scattering, arising from the product of two Boer-Mulders functions, which describe the transverse spin distribution of quarks inside an unpolarized hadron. We find that there is a cos {delta}{phi} angular dependence of the di-jet, with {delta}{phi} the difference of the azimuthal angle of tow jets respectively. In the case of J{sub q}+J{sub q} production, we find that there is a color factor enhancement in the gluonic cross-section due to the multiple initial-/final-state interactions, compared with the result from the standard generalized parton model. We estimate the cos {delta}{phi} asymmetry of the total di-jet production at RHIC, showing that the color factor enhancement in the azimuthal asymmetric cross section of J{sub q}+J{sub q} production will reverse the sign of the asymmetry.

The D0 detector underwent an upgrade to its silicon vertex detector and triggering systems during the transition from Run IIa to Run IIb to maximize its ability to fully exploit Run II at the Fermilab Tevatron. This thesis describes improvements made to the tracking and vertexing algorithms used by the high level trigger in both Run IIa and Run IIb, as well as a search for resonant di-J/{psi} states using both Run IIa and Run IIb data. Improvements made to the tracking and vertexing algorithms during Run IIa included the optimization of the existing tracking software to reduce overall processing time and the certification and testing of a new software release. Upgrades made to the high level trigger for Run IIb included the development of a new tracking algorithm and the inclusion of the new Layer 0 silicon detector into the existing software. The integration of Layer 0 into the high level trigger has led to an improvement in the overall impact parameter resolution for tracks of {approx}50%. The development of a new parameterization method for finding the error associated to the impact parameter of tracks returned by the high level tracking algorithm, in association with the inclusion of Layer 0, has led to improvements in vertex resolution of {approx}4.5 {micro}m. A previous search in the di-J/{psi} channel revealed a unpredicted resonance at {approx}13.7 GeV/c{sup 2}. A confirmation analysis is presented using 2.8 fb{sup -1} of data and two different approaches to cuts. No significant excess is seen in the di-J/{psi} mass spectrum.

Solid di-para-xylyene dimer is sublimed in a sublimation furnace at approximately 100 to 200/sup 0/C and subsequently conducted to a pyrolysis furnace where it is pyrolyzed to the diradical p-xylylene monomer while in the vapor state at approximately 600 degrees C. The diradical monomer is then introduced into a deposition chamber for deposition onto a suitable substrate. The deposition chamber includes electrodes for producing a low pressure plasma through which the diradical monomer passes prior to deposition. The interaction of the diradical monomer with the low pressure plasma results in the formation of poly-p-xylyene film which is exceptionally hard and thermally stable.

The inability to routinely monitor drug-induced phospholipidosis (DIPL) presents a challenge in pharmaceutical drug development and in the clinic. Several nonclinical studies have shown di-docosahexaenoyl (22:6) bis(monoacylglycerol) phosphate (di-22:6-BMP) to be a reliable biomarker of tissue DIPL that can be monitored in the plasma/serum and urine. The aim of this study was to show the relevance of di-22:6-BMP as a DIPL biomarker for drug development and safety assessment in humans. DIPL shares many similarities with the inherited lysosomal storage disorder NiemannâPick type C (NPC) disease. DIPL and NPC result in similar changes in lysosomal function and cholesterol status that lead to the accumulation of multi-lamellar bodies (myeloid bodies) in cells and tissues. To validate di-22:6-BMP as a biomarker of DIPL for clinical studies, NPC patients and healthy donors were classified by receiver operator curve analysis based on urinary di-22:6-BMP concentrations. By showing 96.7-specificity and 100-sensitivity to identify NPC disease, di-22:6-BMP can be used to assess DIPL in human studies. The mean concentration of di-22:6-BMP in the urine of NPC patients was 51.4-fold (p â¤ 0.05) above the healthy baseline range. Additionally, baseline levels of di-22:6-BMP were assessed in healthy non-medicated laboratory animals (rats, mice, dogs, and monkeys) and human subjects to define normal reference ranges for nonclinical/clinical studies. The baseline ranges of di-22:6-BMP in the plasma, serum, and urine of humans and laboratory animals were species dependent. The results of this study support the role of di-22:6-BMP as a biomarker of DIPL for pharmaceutical drug development and health care settings. - Highlights: â¢ A reliable biomarker of drug-induced phospholipidosis (DIPL) is needed for humans. â¢ Di-22:6-BMP is specific/sensitive for DIPL in animals as published in literatures. â¢ The di-22:6-BMP biomarker can be validated for humans via NPC patients. â¢ DIPL

A method and apparatus for forming an improved poly-p-xylylene film. Solid di-para-xylylene dimer is sublimed in a sublimation furnace at approximately 100.degree. to 200.degree. C. and subsequently conducted to a pyrolysis furnace where it is pyrolyzed to the diradical p-xylylene monomer while in the vapor state at approximately 600 degrees C. The diradical monomer is then introduced into a deposition chamber for deposition onto a suitable substrate. The deposition chamber includes electrodes for producing a low pressure plasma through which the diradical monomer passes prior to deposition. The interaction of the diradical monomer with the low pressure plasma results in the formation of poly-p-xylylene film which is exceptionally hard and thermally stable.

The Nerina valley, where Borgo Cerreto is located, is surrounded by the Apennine mount chain at the top of which lies the historical centre of Cerreto di Spoleto. The study is part of a research project aiming at analysing natural disasters and their impact on the Italian cultural heritage. Within the framework of this research project, local seismic records were analysed for both the carbonate ridge and the bordering alluvial valley. The choice of Cerreto di Spoleto as a test site derives from the analysis of Italian seismic hazard maps, obtained in terms of peak ground velocity and taking into account regional geology. The maps highlight the considerable seismic hazard which characterises the Apennine belt and its possible increase due to the effect of alluvial deposits. To this aim, ENEA installed in the 80's an accelerometric array (CODISMA up to 2000 and, in the following years, ETNA; for more detailed description see [1]. The 14 October event, was recorded both at the roof of CSM and at BCT stations. This is important to check the features observed comparing the FAS of acceleration at CSM and BCT during the 26 September events. Unfortunately the station at CSM basement did not record the above mentioned events but several aftershocks were recorded at each array station. Velocimetric records of both ambient noise and small-magnitude earthquakes were analysed in order to identify amplification conditions. The analysis was carried out in the time domain, through directional energy evaluation, and in the frequency domain, through H/V spectral ratios and spectral ratios with respect to a reference station.

Measurements of the di-photon cross section have been made in the central region and are found to be in good agreement with NLO QCD predictions. The cross section of events containing a photon and additional heavy flavor jet have also been measured, as well as the ratio of photon + b to photon + c. The statistically limited sample shows good agreement with Leading Order predictions.

The hydrogenated amorphous silicon a-Si:H films were grown by plasma-enhanced chemical vapor deposition (PECVD) using liquid cyclohexasilane Si{sub 6}H{sub 12} (CHS). The growth rate of a-Si:H was studied as a function of substrate temperatures in the range of 30 C < T < 450 C using deposition conditions that were optimized for monosilane SiH{sub 4}. The same parameters were used for a-Si:H films grown using disilane (Si{sub 2}H{sub 6}) and trisilane (Si{sub 3}H{sub 8}) precursors. It was found that the a-Si:H film growth rate for CHS is lower with respect to those for mono-, di- and trisilane in an Ar plasma. Addition of {approx}10% of H{sub 2} dramatically increases the deposition rate for CHS-based films to {_}nm/min - a 700% increase. The as-deposited films were characterized by FTIR and Raman spectroscopy to probe the hydrogen content and local bonding environment. It was found that the films grown using Ar/H{sub 2} mixtures as carrier gas have a reduced hydrogen content relative to polysilane fragments indicating higher quality amorphous silicon.

The discovery of the Higgs boson would be a major success for the Standard Model (SM) and would provide further insights into the electroweak symmetry breaking mechanism. This report contains the latest results from the D0 and CDF Tevatron experiments on searches for the SM Higgs produced from gluon fusion with H {yields} WW, and in association with a W boson. It also includes searches for a supersymmetric Higgs in the b{bar b} and {tau}{sup +}{tau}{sup -} decay channels. The study of di-boson production at the Tevatron is important to understand backgrounds in high mass Higgs searches. It also provides a test of the SM through the measurement of the production cross section and the gauge boson self couplings. This paper includes measurements of the WW, W{gamma}, and WZ production cross sections, as well as limits on the anomalous couplings associated with the WW{gamma} and WWZ interactions. The results are based on sets of up to 320 pb{sup -1} of data collected by the D0 and CDF experiments at the {bar p}p Tevatron collider, running at a center-of-mass energy of 1.96 TeV.

The thermodynamics and kinetics of hydrogen (H2) release from ethane 1,2-di-amineborane (EDAB, BH3NH2CH2CH2NH2BH3) were measured using Calvet and differential scanning calorimetry (DSC), pressure-composition isotherms, and volumetric gas-burette experiments. The results presented here indicate that EDAB releases ~ 9 wt.% H2 at temperatures ranging from 100 °C to 200 °C in two moderately exothermic steps, approximately -10±1 kJ/mol H2 and -3.8±1 kJ/mol H2. Isothermal kinetic analysis shows that EDAB is more stable than ammonia borane (AB) at temperatures lower than 100°C; however, the rates of hydrogen release are faster for EDAB than for AB at temperatures higher than 120°C. In addition, no volatile impurities in the H2 released by EDAB were detected by mass spectrometry upon heating with 1°C/min to 200°C in a calorimeter.

The authors present a seismic model of a well-exposed carbonate platform-to-basin transition from the Triassic succession at Picco di Vallandro, the Dolomites, northern Italy. The core of this model is a detailed lithologic cross section that represents 1,500 m of stratigraphic section over a distance of 3.5 km. The cross section is based on detailed measured sections, photo interpretation, and careful projection of surface mapping into the plane of section. Samples from the measured sections provide control on velocity and density distribution, and these data were used to generate an impedance model from the cross section. The impedance model was convolved with a zero-phase, 25-Hz peak-frequency wavelet to produce the seismic model. The results illustrate how the platform-to-basin transition might be imaged by conventional seismic reflection data, how the reflections relate to the distribution of lithology and through-going geological surfaces, and how constructive and destructive interference and seismic resolution combine to produce individual reflections.

Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di-tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates (N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/ passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP

The surface chemistry of copper(I)-N,N'-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces has been characterized under ultrahigh vacuum by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy. A series of thermal stepwise conversions were identified, starting with the partial dissociative adsorption of the copper acetamidinate dimers into a mixture of monomers and dimers on the surface. An early dissociation of a C-N bond leads to the production of N-sec-butylacetamidine, which is detected in TPD experiments in three temperature regimes, the last one centered around 480 K. Butene, and a small amount of butane, is also detected above approximately 500 K, and hydrogen production, an indication of dehydrogenation of surface fragments, is observed at 460, 550 and 670 K. In total, only about 10% of the initial copper(I)-N,N'-di-sec-butylacetamidinate adsorbed monolayer decomposes, and only about {approx}3% of carbon is left behind on the surface after heating to high temperatures. The implications of this surface chemistry to the design of chemical film growth processes using copper acetamidinates as precursors are discussed.

A search for directly produced Supersymmetric Higgs Bosons has been performed in the di-tau decay channel in 86.3 {+-} 3.5 pb{sup -1} of data collected by CDF during Run1b at the Tevatron. They search for events where one tau decays to an electron and the other tau decays hadronically. They perform a counting experiment and set limits on the cross section for Higgs production in the high tan {beta} region of the m{sub A}-tan {beta} plane. For a benchmark parameter space point where m{sub A} = 100 and tan {beta} = 50, they set a 95% confidence level upper limit at 891 pb compared to the theoretically predicted cross section of 122 pb. For events where the tau candidates are not back-to-back, they utilize a di-tau mass reconstruction technique for the first time on hadron collider data. Limits based on a likelihood binned in di-tau mass from non-back-to-back events alone are weaker than the limits obtained from the counting experiment using the full di-tau sample.

A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH3-, and OH- diphenyl ethers has been explored over Ni/SiO2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC6H4O* (adsorbed), which is then cleaved to phenol (C6H5O* with added H*) and H2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC6H4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h-1) > diphenyl ether (26 h-1) > di-p-tolyl ether (1.3 h-1), in line with the increasing apparent activation energies, ranging from 93 kJâmol-1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJâmol-1) to di-p-tolyl ether (105 kJâmol-1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R

The title complexes, Diaquadi(2,2`-bipyridine)Di(Dichloroacetato)Lanthanide (III) Monodichloroacetato [Ln(CHCI{sub 2}COO){sub 2}(2,2`-bipy){sub 2}(H{sub 2}O){sub 2}]{sup +}(CHCI{sub 2}COO){sup -}(Ln=Dy, Ho, Tm, Er, Yb) were obtained and characterized. [Er(CHCI{sub 2}COOO){sub 2}(2,2`-bipy){sub 2} (H{sub 2}O){sub 2}]+(CHCI{sub 2}COO){sup -} crystallizes in the monoclinic space group P2{sub 1}/n with Z=4. Cell dimensions are a=15.886 (9), b=13.758(2), c=16.343(4) {angstrom}, {Beta}=113.31(3){degrees}, and the structure was refined to an R of 0.049 for 3415 observed reflections. The Er(III) ion exhibits a distorted, square antiprismatic configuration. Four N atoms of 2,2`-bipy and four O atoms from two dichloroacetato and two water ligands are coordinated. One dichloroacetato group lies outside the polyhedron and is connected with water ligands by hydrogen bonds.

A strong effect of a moderately elevated surface temperature on net carbon deposition and deuterium co-deposition in the DIII-D divertor was observed under detached conditions. A DiMES sample with a gap 2 mm wide and 18 mm deep was exposed to lower-single-null (LSN) L-mode plasmas first at room temperature, and then at 200 C. At the elevated temperature, deuterium co-deposition in the gap was reduced by an order of magnitude. At the plasma-facing surface of the heated sample net carbon erosion was measured at a rate of 3 nm/s, whereas without heating net deposition is normally observed under detachment. In a related experiment three sets of molybdenum mirrors recessed 2 cm below the divertor floor were exposed to identical LSN ELMy H-mode discharges. The first set of mirrors exposed at ambient temperature exhibited net carbon deposition at a rate of up to 3.7 nm/s and suffered a significant drop in reflectivity. In contrast, two other mirror sets exposed at elevated temperatures between 90 C and 175 C exhibited practically no carbon deposition.

Detailed geologic cross sections, augmented by laboratory calibration of lithology and acoustic impedance, have been used to produce synthetic reflection seismic sections of a carbonate foreslope-to-basin transition. Two areas from the Picco di Vallandro region of the Dolomite Alps were modeled: a progradational section and a retrogradational (backstepping) section. The resulting models show how these complex areas of strata interfingering might be displayed on conventional reflection seismic lines. In the area of progradation, rapid stratigraphic thinning below seismic detectibility, coupled with abrupt impedance changes, produces a reflection discontinuity between steeply dipping reflections of the foreslope and gently dipping paralle reflections of the basin section. This apparent downlap surface marks the toe-of-slope for successive clinoforms but dose not correspond to a discrete stratigraphic surface. In the backstepping example, similar stratigraphic thinning and impedance changes create an apparent onlap surface. Wavelet interference causes complications in both examples. These models indicate how stratigraphic complexity can be simplified by the seismic reflection process and suggest that caution should be exercised when using seismic data to construct general models in areas of complex depositional geometries and rapidly changing facies.

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H{sub 2}O (or D{sub 2}O) confined in 28 Ã pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0â90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement, but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Ã . The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.

objective of this task is to perform bench scale testing on various frits that have been used at DWPF or in test programs at SRNL to determine the quantity of de-ionized (DI) water required to mitigate dusting per mass basis of frit. The quantity of DI water required was determined visually by observing the effluent port of the mixer, and DI water addition was made to the point where no visible dust was observed leaving the effluent port. A total of eight different frits were selected for testing. Secondary objectives in this task include the following: (1) Video taping of the de-dusting procedure, (2) Particle size distribution analyses of the dry and wetted frits at the weight fraction of water required for de-dusting, (3) Plate flow tests to determine angle of flow and quantity of material remaining on plate at 90 degrees, (4) Microscopy of dry and wetted frit, and (5) Effect of excess water for selected frits on plate flow. The above analyses were performed within one hour of water addition, to minimize the effect of evaporative water losses. To better understand the size of dust particles, perform settling tests on selected frits and capture the fines. Analyze the fines for particle size distribution. Finally, it is expected that the surface area of frit is an important parameter in the quantity of water required for dust mitigation. An analysis of particle size distribution (PSD) data of as-received frit analyzed by SRNL over the past two to three years will be performed to determine the variation in the distribution of as-received frit. The following objectives were stated in the Technical Task Request4 as objectives that given adequate time would provide insight in helping DWPF in assessing equipment or processes for de-dusting and processing of dry frit. Due to time constraints, commercial methods for dedusting are provided. These results are detailed in section 3.7. Obtain design information from Hanford with respective to equipment used for dedusting. Suggestions

Fuel processing systems for low temperature polymer electrolyte membrane (PEM) fuel cell systems require control of the carbon monoxide concentration to less than 100 ppm to 10 ppm in the anode feed. Conventional hydrocarbon fuel processors use a water-gas shift (WGS) reactor to react CO with water to form H2 and reduce the CO concentration. The CO conversion is limited by equilibrium at the outlet temperature of the WGS reactor. The WGS outlet CO concentration can range from over 1% to 2000 ppm depending on the system and its operating parameters. At these concentrations, CO poisons low temperature PEM fuel cells and the concentrations needs to be reduced further.

it is common for facilities to have a lobby with a display loop while also requiring an option for guided tours. Existing solutions have required expensive hardware and awkward software. Our solution is relative low cost as it runs on an iPad connected to an external monitor, and our software provides an intuitive touch interface. The media files are downloaded from a web server onto the device allowing a mobile option (e.g. displays at conferences). Media may include arbitrary sequences of images, movies or PDF documents. Tour guides can select different tracks of slides to display and the presentation will return to the default loop after a timeout.

it is common for facilities to have a lobby with a display loop while also requiring an option for guided tours. Existing solutions have required expensive hardware and awkward software. Our solution is relative low cost as it runs on an iPad connected to an external monitor, and our software provides an intuitive touch interface. The media files are downloaded from a web server onto the device allowing a mobile option (e.g. displays at conferences).moreÂ Â» Media may include arbitrary sequences of images, movies or PDF documents. Tour guides can select different tracks of slides to display and the presentation will return to the default loop after a timeout.Â«Â less

The selective separation of uranium(VI) in the first cycle of the GANEX process is operated by a hydrometallurgical process using a monoamide extractant DEHiBA (N,N-di-(2-ethylhexyl)isobutyramide). Distribution ratios of uranium(VI) and nitric acid in 1 M DEHiBA/HTP were determined with macro-concentrations of uranium, and the experimental data were modelled by taking into account the activity coefficients of the constituents in aqueous phases. A flowsheet was designed and tested in a countercurrent process in laboratory-scale mixer-settlers on a surrogate U(VI)/HNO 3 feed. More than 99.999% of the uranium was recovered. (authors)

The novel water soluble bidentate phosphine ligand 1,3-bis(di-2-pyridylphosphino)propane (d2pypp) has been synthesized by a convenient route involving treatment of 2-pyridyllithium with Cl{sub 2}P(CH{sub 2}){sub 3}PCl{sub 2} and isolation in crystalline form as the hydrochloride salt. The synthesis of the precursor Cl{sub 2}P(CH{sub 2}){sub 3}PCl{sub 2} has been optimized by the use of triphosgene as the chlorinating agent. The 2:1 and 1:2 AuCl:d2pypp adducts have been synthesized and characterized by NMR spectroscopy and single crystal X-ray studies, and shown to be of the form (AuCl){sub 2}({mu}-d2pypp-P,P{prime}) and Au(d2pypp-P,P{prime}){sub 2}Cl(-3.75H{sub 2}O), respectively. The latter is more lipophilic than analogous 1:2 adducts of gold(I) chloride with the diphosphine ligands 1,2-bis(di-n-pyridylphosphino)ethane (dnpype) for n = 2, 3 and 4, based on measurement of the n-octanol-water partition coefficient (log P = -0.46). A single crystal structure determination of the 1:2 Au(I) complex of the 3-pyridyl ethane ligand shows it to be of the form [Au(d3pype-P,P{prime}){sub 2}]Cl {center_dot} 5H{sub 2}O. The in vitro cytotoxic activity of [Au(d2pypp){sub 2}]Cl was assessed in human normal and cancer breast cells and selective toxicity to the cancer cells found. The significance of these results to the antitumour properties of chelated 1:2 Au(I) diphosphine complexes is discussed.

The goal of the work performed during the contract period was to establish the ability to study soot and NO within the combustion chamber of a DI Diesel engine and to couple these measurements with actual exhaust emissions. This work was motivated by the need to obtain a more complete understanding of the particulate/NO{sub X} trade-off, observed in Diesel engines, to aid engine designers in meeting emissions limits. In order to achieve the desired goal, an optically accessible DI Diesel engine was designed and constructed. Also, planar imaging methods for imaging soot and NO were developed in laboratory flames and were then applied to the engine. For the study of soot, planar Mie scattering was used and a polarization ratio method was investigated to distinguish soot from fuel droplets. The Mie scattering technique proved to be well suited for the engine, and extensive results were obtained. In order to observe NO, planar laser induced fluorescence was used and it was successfully applied in the engine. In addition to these techniques, high speed combustion photography and shadowgraph photography were applied to obtain general characteristics of the combustion process. As a final diagnostic, actual engine emissions were measured. This report begins with a brief discussion of the problem under investigation and a summary of other studies of the NO{sub x}/particulate trade-off. Following these sections is a summary of the accomplishments and results from the present study. Finally, detailed results are presented through the six technical papers which were written during the contract period; these papers are appended to the report.

A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte, and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula (in an uncharged state): ##STR1## where R.sub.1 is selected from the group consisting of H, OCH.sub.3, OCH.sub.2 CH.sub.3, and OCH.sub.2 phenyl, and R.sub.2 is selected from the group consisting of OCH.sub.3, OCH.sub.2 CH.sub.3, OCH.sub.2 phenyl, and O.sup.- Li.sup.+ ; and (b) a di-anisole compound having the general formula (in an uncharged state): ##STR2## where R is selected from the group consisting of -OCH.sub.3 and -CH.sub.3, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH.sub.3 (methoxy) or its lithium salt --O.sup.- Li.sup.+. The lithium salt of the di-anisole is the preferred form of the redox shuttle additive because the shuttle anion will then initially have a single negative charge, it loses two electrons when it is oxidized at the cathode, and then moves toward the anode as a single positively charged species where it is then reduced to a single negatively charged species by gaining back two electrons.

Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300?°C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M?=?Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200?°C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18?nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

In order to help design a high-power-density (HPD) low-heat-rejection (LHR) high-injection-fuel (HIP) direct-injection compression-ignition engine (DI-CI), two main methods were employed: (1) engine performance analysis; and (2) in-cylinder imaging. In the performance analysis, a Cummins 903 engine was used. The range of air/fuel ratio studied was from 18-1 to over 35-1, the injection pressure investigated was as high as 30,625 psi (210 Mpa) under varied intake air temperature over 150 deg C. In the in-cylinder imaging, a separate optical single-cylinder Cummins 903 engine was used. A high-speed four-color IR digital imaging system was greatly improved during this contract period. New spectrometric methods were developed to simultaneously determine the distributions of temperature, water vapor and soot concentrations. In addition, a new data analysis and presentation method has been developed. The performance analysis results are reported in two parts: a preliminary report as included in Appendix-I and an additional set of results (Appendix-III). Some of the in-cylinder imaging results, which are now being captured by the improved 515 after incorporating with new electronic packages (designed and fabricated in the laboratory), are included with discussions.

L{sub 2,3}-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L{sub 2,3}-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L{sub 2,3}-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.

The compound (bpy)2MnIII(mu-O)2MnIV(bpy)2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single CrVI charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of MnIII(mu-O)2MnIV demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of CrVI centers. The FT-Raman spectrum upon visible light excitation of the CrVI-OII --> CrV-OI ligand-to-metal charge-transfer reveals electron transfer from MnIII(mu-O)2MnIV (Mn-O stretch at 700 cm-1) to CrVI, resulting in the formation of CrV and MnIV(mu-O)2MnIV (Mn-O stretch at 645 cm-1). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (DELTA Eo = -0.6 V) remain after several minutes, which points to spatial separation of CrV and MnIV(mu-O)2MnIV as a consequence of hole (OI) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well defined transition metal molecular units, with the ultimate goal of performing endothermic, multi-electron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.

This document details the distinction between using PAO (4 cSt polyalphaoelfin) oil instead of DOP (di-octyl phthalate) oil for measuring the aerosol capture of filters. This document is developed to justify the use of PAO rather than DOP for evaluating the performance of filters in the SAVY 4000 and Hagan containers. The design criteria (Anderson et al, 2012) for purchasing SAVY 4000 containers and the Safety Analysis Report for the SAVY 4000 Container Series specified that the filter must âcapture greater than 99.97% of 0.45 Î¼m mean diameter dioctyl phthalate (DOP) aerosol at the rated flow with a DOP concentration of 65Â±15 micrograms per liter.âThis corresponds to a leakage percent of 0.03% (3.0x10-2). The density of DOP oil is 985 kg/m3 and the density of PAO oil is 819 kg/m3. ATI Test Inc measured the mass mean diameter of aerosol distributions produced by a single Laskin type III-A nozzle operating at a 20 psig air pressure as 0.563 Î¼m for DOP oil and 0.549 Î¼m for PAO oil. (See Appendix A.) For both types of oil in this document, the single fiber method calculated the leakage percent to be 4.4x10-5 for DOP oil and 4.7x10-5 for PAO oil. Although the percent error between these two quantities is 7.7%, these calculated leakage percent values are more than two orders of magnitude less than the criterion specified in the SAVY canister SAR. As a point of reference, the photometer used to measure the SAVY canister filter performance cannot resolve values for the leakage percent below 1.0x10-5. Additionally, over a range of particle sizes from 0.01 Î¼m to 3.0 Î¼m, there was less than 4.0x10-5 error between the calculated filter efficiency for the two types of oil at any particular particle size diameter. In conclusion, the difference between using DOP and PAO for testing SAVY canister filters is of inconsequential concern.

Four N,N'-dialkyl-N,N'-diphenyl-pyridine-2,6- di-carboxy-amides (R-PDA; R butyl, octyl, decyl, dodecyl) were newly synthesized and were applied to extraction chromatography as extractant to attain the separation of actinides(III) from high level radioactive waste containing lanthanides(III). R-PDA was successfully impregnated into XAD-4 resin. It was found that (i) the leakage of R-PDA from XAD-4 resin was suppressed with an increase of the length of the alkyl groups in R-PDA, while the leakage for each adsorbent resin was promoted with an increase of HNO{sub 3} concentration in the aqueous phase and (ii) Oc-PDA or De-PDA/XAD-4 resin exhibits moderate separation ability of actinides(III) from lanthanides(III) at relatively high HNO{sub 3} concentration. (authors)

We report on large modifications of current-induced spin-orbit torques in a gated Pt/Co/Gd-oxide microstrip due to voltage-driven O{sup 2â} migration. The Slonczewski-like and field-like torques are quantified using a low-frequency harmonic technique based on the polar magneto-optical Kerr effect. Voltage-induced oxidation of Co enhances the Slonczewski-like torque by as much as an order of magnitude and simultaneously reduces the anisotropy energy barrier by a factor of â¼5. Such magneto-ionic tuning of interfacial spin-orbit effects may significantly enhance the efficiency of magnetization switching and provide additional degrees of freedom in spintronic devices.

This study reports the interaction of methanol, ethanol, 1-propanol, and 2-propanol with well-ordered CeO{sub 2}(111) thin film surfaces. All of the alcohols adsorb at low temperature by forming alkoxy and hydroxyl species on the surface. On fully oxidized CeO{sub 2}(111), recombination occurs between some of the alkoxys and hydroxyls, resulting in alcohol desorption near 220 K. At the same temperature, some of the surface hydroxyls disproportionate to produce water and the loss of lattice O. The remaining alkoxys react above 550 K. The primary alcohols favor dehydrogenation products (aldehydes). There is a net loss of O from the system, resulting in a reduction of the ceria. The secondary alcohol, 2-propanol, undergoes primarily dehydration, producing propene with no net change in the cerium oxidation state. Reduced CeO{sub x}(111) competes with the gaseous products for available O. Little or no water is produced. The reaction selectivity for the C{sub 2} and C{sub 3} alcohols shifts toward favoring dehydration products. The loss of O from the alcohols leads to oxidation of the reduced ceria. Compared with the oxidized surface, the alkene desorption shifts to lower temperature, whereas the aldehyde desorption shifts to higher temperature. This indicates that, on the reduced surface, it is easier to break the C-O bond but more difficult to break the O-substrate bond.

Fuel Processor systems generate hydrogen for fuel cell systems from hydrocarbon fuels such as gasoline for automotive fuel cell systems and natural gas for stationary fuel cell systems. These fuel processor systems must remove any contaminants to levels that won't poison the fuel cell before the outlet hydrogen-rich gas stream can be used by the fuel cell to generate electricity. Carbon monoxide is a contaminant that must be removed to levels of < 100 ppm or < 10 ppm depending on the CO tolerance of the fuel cell. Typically, the last unit operation in a fuel processor is a preferential oxidation reactor or a selective oxidation reactor, which removes CO by oxidizing it to form C02. These are catalytic reactors where the catalyst and operating conditions are selected so that the oxidation rate of the carbon monoxide is higher than the oxidation rate of hydrogen, even though the hydrogen is present at much higher concentrations (> 30%) than carbon monoxide which is present at trace concentrations (< 1%).

The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 â¶). Acta Cryst. B66, 615â621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@eculeâs 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: NâHâ¯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.

Textured transparent conductors are widely used in thin-film silicon solar cells. They lower the reflectivity at interfaces between different layers in the cell and/or cause an increase in the path length of photons in the Si absorber layer, which both result in an increase in the number of absorbed photons and, consequently, an increase in short-circuit current density (J{sub sc}) and cell efficiency. Through optical simulations, we recently obtained strong indications that texturing of the transparent conductor in copper indium gallium (di-)selenide (CIGS) solar cells is also optically advantageous. Here, we experimentally demonstrate that the J{sub sc} and efficiency of CIGS solar cells with an absorber layer thickness (d{sub CIGS}) of 0.85 Î¼m, 1.00 Î¼m and 2.00 Î¼m increase through application of a moth-eye textured resist with a refractive index that is sufficiently similar to AZO (n{sub resist} = 1.792 vs. n{sub AZO} = 1.913âat 633 nm) to avoid large optical losses at the resist-AZO interface. On average, J{sub sc} increases by 7.2%, which matches the average reduction in reflection of 7.0%. The average relative increase in efficiency is slightly lower (6.0%). No trend towards a larger relative increase in J{sub sc} with decreasing d{sub CIGS} was observed. Ergo, the increase in J{sub sc} can be fully explained by the reduction in reflection, and we did not observe any increase in J{sub sc} based on an increased photon path length.

The plasticizer di(2-ethylhexyl) phthalate (DEHP) is suspected to induce antiandrogenic effects in men via its metabolite mono(2-ethylhexyl) phthalate (MEHP). However, there is only little information on the kinetic behavior of DEHP and its metabolites in humans. The toxikokinetics of DEHP was investigated in four male volunteers (2861 y) who ingested a single dose (645 ± 20 ?g/kg body weight) of ring-deuterated DEHP (DEHP-D{sub 4}). Concentrations of DEHP-D{sub 4}, of free ring-deuterated MEHP (MEHP-D{sub 4}), and the sum of free and glucuronidated MEHP-D{sub 4} were measured in blood for up to 24 h; amounts of the monoesters MEHP-D{sub 4}, ring-deuterated mono(2-ethyl-5-hydroxyhexyl) phthalate and ring-deuterated mono(2-ethyl-5-oxohexyl) phthalate were determined in urine for up to 46 h after ingestion. The bioavailability of DEHP-D{sub 4} was surprisingly high with an area under the concentration-time curve until 24 h (AUC) amounting to 50% of that of free MEHP-D{sub 4}. The AUC of free MEHP-D{sub 4} normalized to DEHP-D{sub 4} dose and body weight (AUC/D) was 2.1 and 8.1 times, that of DEHP-D{sub 4} even 50 and 100 times higher than the corresponding AUC/D values obtained earlier in rat and marmoset, respectively. Time courses of the compounds in blood and urine of the volunteers oscillated widely. Terminal elimination half-lives were short (4.36.6 h). Total amounts of metabolites in 22-h urine are correlated linearly with the AUC of free MEHP-D{sub 4} in blood, the parameter regarded as relevant for risk assessment. -- Highlights: ? After DEHP intake, DEHP and MEHP in blood show oscillating time courses. ? Dose-related blood levels of DEHP are 50 times higher in humans than in rats. ? Dose-related blood levels of free MEHP are 2 times higher in humans than in rats. ? Elimination of DEHP and its metabolites is short with half-lives of 4.3-6.6 h.

A primary alkyl amine and an alcohol of up to 12 carbon atoms are reacted at low temperature (50.degree.-250.degree. C.) over specific catalysts (alkali-treated catalysts generally or binary Cu/ZnO and Pd/SiO.sub.2 systems, with or without alkali treatment) to produce, with good selectivity, secondary and tertiary alkylamines of the general formula, R.sub.1 N(R.sub.2).sub.2, wherein R.sub.1 is a lower alkyl or an aryl group, and R.sub.2 is hydrogen or another lower alkyl or aryl group, with at least one of R.sub.2 's being an alkyl or aryl group.

The compound K2Ce(SO4)3 x H2O (I) was obtained in a study of the system Ce(SO4)2-K2SO4-H2O4-HO2 at 50-150C (1). The refined unit-cell parameters are: a = 20.600(3), b = 7.0744 (6), c = 18.583(3) A, US = 126.083(8), V = 2189(1) AT, Z = 8, rho/sub calc/ = 3.202(2) g/cmT, space group C2. The previously given unit-cell parameters are related to those given here by the matrices 100/010/0.5 0 1 and 100/010/-1 0-1. The intensities of 3416 independent reflections (3363 with I greater than or equal to 2sigma) and the unit cell parameters were measured on a Syntex P21 four-circle automatic diffractometer (lambdaMoK , theta/2 theta scanning at variable rate from 4 to 29.3 deg/min to theta = 60). The structural calculations were done on a Nova 1200 minicomputer by means of the Syntex XTL programs and on an ES 1022 computer by means of the Struktura programs. They used the heavy atom method; the final refinement over 3240 reflections (R = 0.071) was made allowing for the anisotropy of the thermal vibrations of the atoms.

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeOâ cubes and CeOâ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeOâ-cubes > RhPd/CeOâ -rods > RhPd/CeOâ- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeOâ-cubes and RhPd/CeOâ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

We have studied the reaction of ethanol and water over NiCeO2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on NiCeO2-x(111) at varying Ce³? concentrations (CeO1.82.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria. Ni? is themore »active phase leading to both the CC and CH cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni?C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metalsupport interaction between nickel and ceria that facilitates oxygen transfer.« less

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeOâ cubes and CeOâ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeOâ-cubes > RhPd/CeOâ -rods > RhPd/CeOâ- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeOâ-cubes and RhPd/CeOâ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -moreÂ Â» oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceriaÂ«Â less

The characterization and implementation of solution-processed, wide bandgap nickel oxide (NiO{sub x}) hole-selective interlayer materials used in bulk-heterojunction (BHJ) organic photovoltaics (OPVs) are discussed. The surface electrical properties and charge selectivity of these thin films are strongly dependent upon the surface chemistry, band edge energies, and midgap state concentrations, as dictated by the ambient conditions and film pretreatments. Surface states were correlated with standards for nickel oxide, hydroxide, and oxyhydroxide components, as determined using monochromatic X-ray photoelectron spectroscopy. Ultraviolet and inverse photoemission spectroscopy measurements show changes in the surface chemistries directly impact the valence band energies. O?-plasma treatment of the as-deposited NiO{sub x} films was found to introduce the dipolar surface species nickel oxyhydroxide (NiOOH), rather than the p-dopant Ni?O?, resulting in an increase of the electrical band gap energy for the near-surface region from 3.1 to 3.6 eV via a vacuum level shift. Electron blocking properties of the as-deposited and O?-plasma treated NiO{sub x} films are compared using both electron-only and BHJ devices. O?-plasma-treated NiO{sub x} interlayers produce electron-only devices with lower leakage current and increased turn on voltages. The differences in behavior of the different pretreated interlayers appears to arise from differences in local density of states that comprise the valence band of the NiO{sub x} interlayers and changes to the band gap energy, which influence their hole-selectivity. The presence of NiOOH states in these NiO{sub x} films and the resultant chemical reactions at the oxide/organic interfaces in OPVs is predicted to play a significant role in controlling OPV device efficiency and lifetime.

A method of producing and purifying promethium-147 including the steps of: irradiating a target material including neodymium-146 with neutrons to produce promethium-147 within the irradiated target material; dissolving the irradiated target material to form an acidic solution; loading the acidic solution onto a chromatographic separation apparatus containing HDEHP; and eluting the apparatus to chromatographically separate the promethium-147 from the neodymium-146.

Diesel engines are far more efficient than gasoline engines of comparable size, and emit less greenhouse gases that have been implicated in global warming. In 2000, the US EPA proposed very stringent emissions standards to be introduced in 2007 along with low sulfur (< 15 ppm) diesel fuel. The California Air Resource Board (CARB) has also established the principle that future diesel fueled vehicles should meet the same low emissions standards as gasoline fueled vehicles and the EPA followed suit with its Tier II emissions regulation. Achieving such low emissions cannot be done through engine development and fuel reformulation alone, and requires application of NOx and particulate matter (PM) aftertreatment control devices. There is a widespread consensus that NOx adsorbers and particulate filter are required in order for diesel engines to meet the 2007 emissions regulations for NOx and PM. In this paper, the key exhaust characteristics from an advanced diesel engine are reviewed. Development of the NOx adsorber technology is discussed. Spectroscopic techniques are applied to understand the underlying chemical reactions over the catalyst surface during NOx trapping and regeneration periods. In-situ surface probes are useful in providing not only thermodynamic and kinetics information required for model development but also a fundamental understanding of storage capacity and degradation mechanisms. The distribution of various nitration/sulfation species is related to surface basicity. Surface displacement reactions of carbonates also play roles in affecting the trapping capability of NOx adsorbers. When ultralow-S fuel is used as a reductant during the regeneration, sulfur induced performance degradation is still observed in an aged catalyst. Other possible sources related to catalyst deactivation include incomplete reduction of surface nitration, coke formation derived from incomplete hydrocarbon burning, and lubricant formulations. Sulfur management and the direction of future work for the successful implementation of such integrated engine and aftertreatment technology are discussed. SAE Paper SAE-2002-01-2889 {copyright} 2002 SAE International. This paper is published on this website with permission from SAE International. As a user of this website, you are permitted to view this paper on-line, download this pdf file and print one copy of this paper at no cost for your use only. The downloaded pdf file and printout of this SAE paper may not be copied, distributed or forwarded to others or for the use of others.

The helecity amplitudes of the subprocess gg{yields}{gamma}{gamma} via scalar unparticles intermediate states are calculated. The differential cross section is compared to that of the standard model. Phenomenological implications are also discussed.

An experimental study was conducted using the dumping technique (total cylinder sampling) to produce cylinder mass-averaged nitric oxide histories. Data were taken using a four stroke diesel research engine employing a quiescent chamber, high pressure direct ijection fuel system, and simulated turbocharging. Two fuels were used to determine fuel cetane number effects. Two loads were run, one at an equivalence ratio of 0.5 and the other at a ratio of 0.3. The engine speed was held constant at 1500 rpm. Under the turbocharged and retarded timing conditions of this study, nitric oxide was produced up to the point of about 85% mass burned. Two different models were used to simulate the engine mn conditions: the phenomenological Hiroyasu spray-combustion model, and the three dimensional, U.W.-ERO modified KIVA-lI computational fluid dynamic code. Both of the models predicted the correct nitric oxide trend. Although the modified KIVA-lI combustion model using Zeldovich kinetics correctly predicted the shapes of the nitric oxide histories, it did not predict the exhaust concentrations without arbitrary adjustment based on experimental values.

Gasoline direct injection (GDI) engines can offer better fuel economy and higher performance over their port fuel-injected (PFI) counterparts, and are now appearing in increasingly more U.S. and European vehicles. Small displacement, turbocharged GDI engines are replacing large displacement engines, particularly in light-duty trucks and sport utility vehicles, in order for manufacturers to meet the U.S. fuel economy standards for 2016. Furthermore, lean-burn GDI engines can offer even higher fuel economy than stoichiometric GDI engines and have overcome challenges associated with cost-effective aftertreatment for NOx control. Along with changes in gasoline engine technology, fuel composition may increase in ethanol content beyond the current 10% due to the recent EPA waiver allowing 15% ethanol. In addition, the Renewable Fuels Standard passed as part of the 2007 Energy Independence and Security Act (EISA) mandates the use of biofuels in upcoming years. GDI engines are of environmental concern due to their high particulate matter (PM) emissions relative to port-fuel injected (PFI) gasoline vehicles; widespread market penetration of GDI vehicles may result in additional PM from mobile sources at a time when the diesel contribution is declining. In this study, we characterized particulate emissions from a European certified lean-burn GDI vehicle operating on ethanol-gasoline blends. Particle mass and particle number concentration emissions were measured for the Federal Test Procedure urban driving cycle (FTP 75) and the more aggressive US06 driving cycle. Particle number-size distributions and organic to elemental carbon ratios (OC/EC) were measured for 30 MPH and 80 MPH steady-state operation. In addition, particle number concentration was measured during wide open throttle accelerations (WOTs) and gradual accelerations representative of the FTP 75. Fuels included certification gasoline and 10% (E10) and 20% (E20) ethanol blends from the same supplier. The particle mass emissions were approximately 3 and 7 mg/mile for the FTP75 and US06, respectively, with lower emissions for the ethanol blends. The data are compared to a previous study on a U.S.-legal stoichiometric GDI vehicle operating on the same ethanol blends. The lean-burn GDI vehicle emitted a higher number of particles, but had an overall smaller average size. Particle number per mile decreased with increasing ethanol content for the transient tests. For the 30 and 80 mph tests, particle number concentration decreased with increasing ethanol content, although the shape of the particle size distribution remained the same. Engine-out OC/EC ratios were highest for the stoichiometric GDI vehicle with E20, but tailpipe OC/EC ratios were similar for all vehicles.

For reducing the exhaust emissions and improving the ignition characteristics, the effect of pilot injection was investigated experimentally in a turbocharged direct injection diesel engine. The pilot injection quantity was varied by changing the seat diameter of the Doge plunger installed in the newly developed pilot injector while the separation period between the beginning of pilot injection and that of main injection was fixed at a short interval in the present experiment. The pilot injection effect on combustion was compared with the case of normal injection in two fuel oils with the cetane indexes of 53 and 40-respectively. The pilot injection showed some significant effects on improving the ignition characteristics and fuel consumption as follows: (1) The pilot ignition delay and the main ignition delay were about half of the ignition delay of the normal injection respectively. (2) The lower fuel consumption and NOx could be attained by the pilot injection at the retarded injection timing, especially under the lower load condition. (3) The trade-off relationship between the specific fuel consumption and NOx was significantly improved by the pilot injection. (4) In the present short pilot-main interval, a small amount of pilot quantity was recommended to reduce NOx and fuel consumption without deteriorating smoke density. 12 refs., 16 figs., 1 tab.

April 6, 2015 1 SAFETY SYSTEM OVERSIGHT ANNUAL AWARD PROGRAM OBJECTIVE The Safety System Oversight (SSO) Annual Award is a special award designed to recognize superior or exemplary service by an employee who has performed SSO functions. This special award program has been established in accordance with the requirements of Department of Energy (DOE) Order 331.1C, Employee Performance Management and Recognition Program. SAFETY SYSTEM OVERSIGHT ANNUAL AWARD The SSO Annual Award recipient is

A low mass Standard Model Higgs boson should be visible at the Large Hadron Collider through its production via gluon-gluon fusion and its decay to two photons. We compute the interference of this resonant process, gg {yields} H {yields} {gamma}{gamma}, with the continuum QCD background, gg {yields} {gamma}{gamma} induced by quark loops. Helicity selection rules suppress the effect, which is dominantly due to the imaginary part of the two-loop gg {yields} {gamma}{gamma} scattering amplitude. The interference is destructive, but only of order 5% in the Standard Model, which is still below the 10-20% present accuracy of the total cross section prediction. We comment on the potential size of such effects in other Higgs models.

Subcommittee on Energy and Power Committee on Energy and Commerce U.S. House of Representatives February 11, 2015 Chairman Upton, Ranking Member Pallone, Chairman Whitfield, Ranking Member Rush, and Members of the Subcommittee, thank you for the opportunity to appear before you today to discuss the Department of Energy's (DOE) Budget Request for fiscal year (FY) 2016. I appreciate the opportunity to discuss how the Budget Request advances the Department of Energy's missions. Advancing Nuclear

In the advent of the installation of a PIT-tag interrogation system in the Cascades Island fish ladder at Bonneville Dam (BON), and other CRB dams, this overview describes in general terms what can and cannot be estimated under seven different scenarios of adult PIT-tag detection capabilities in the CRB. Moreover, this overview attempted to identify minimal adult PIT-tag detection configurations required by the ten threatened Columbia River Basin (CRB) chinook and steelhead ESUs. A minimal adult PIT-tag detection configuration will require the installation of adult PIT-tag detection facilities at Bonneville Dam and another dam above BON. Thus, the Snake River spring/summer and fall chinook salmon, and the Snake River steelhead will require a minimum of three dams with adult PIT-tag detection capabilities to guarantee estimates of ''ocean survival'' and at least of one independent, in-river returning adult survival (e.g., adult PIT-tag detection facilities at BON and LGR dams and at any other intermediary dam such as IHR). The Upper Columbia River spring chinook salmon and steelhead will also require a minimum of three dams with adult PIT-tag detection capabilities: BON and two other dams on the BON-WEL reach. The current CRB dam system configuration and BPA's and COE's commitment to install adult PIT-tag detectors only in major CRB projects will not allow the estimation of an ''ocean survival'' and of any in-river adult survival for the Lower Columbia River chinook salmon and steelhead. The Middle Columbia River steelhead ESU will require a minimum of two dams with adult PIT-tag detection capabilities: BON and another upstream dam on the BON-McN reach. Finally, in spite of their importance in terms of releases, PIT-tag survival studies for the Upper Willamette chinook and Upper Willamette steelhead ESUs cannot be perform with the current CRB dam system configuration and PIT-tag detection capabilities.

We present a new approach to coronal dimming detection using the COronal DImming Tracker tool (CODIT), which was found to be successful in locating and tracking multiple dimming regions. This tool, an extension of a previously developed coronal hole tracking software, allows us to study the properties and the spatial evolution of dimming regions at high temporal and spatial cadence from the time of their appearance to their disappearance. We use Solar Dynamics Observatory/Atmospheric Imaging Assembly 193 A wavelength observations and Helioseismic and Magnetic Imager magnetograms to study dimmings. As a demonstration of the detection technique we analyzed six recurrences of a dimming observed near AR 11305 between 2011 September 29 and October 2. The dimming repeatedly appeared and formed in a similar way, first expanding then shrinking and occasionally stabilizing in the same location until the next eruption. The dimming areas were studied in conjunction with the corresponding flare magnitudes and coronal mass ejection (CME) masses. These properties were found to follow a similar trend during the observation period, which is consistent with the idea that the magnitude of the eruption and the CME mass affect the relative sizes of the consecutive dimmings. We also present a hypothesis to explain the evolution of the recurrent single dimming through interchange reconnection. This process would accommodate the relocation of quasi-open magnetic field lines and hence allow the CME flux rope footpoint (the dimming) to expand into quiet-Sun regions. By relating the properties of dimmings, flares, and CMEs we improve our understanding of the magnetic field reconfiguration caused by reconnection.

This study was mainly focused on evaluating the route-specific passage and migration success of steelhead kelts passing downstream through The Dalles Dam (TDA) and Bonneville Dam (BON) at Columbia River (CR) river kilometers 309 and 234 respectively. Oregon Department of Fish and Wildlife (ODFW) personnel collected, tagged and released out-migrating steelhead kelts in the tributaries of the Deschutes River, 15 Mile Creek and Hood River between April 14 and June 4, 2012. A PIT tag was injected into each keltâs dorsal sinus whereas a Juvenile Salmon Acoustic Telemetry System (JSATS) acoustic micro-transmitter was attached to an external FLoy T-bar tag and inserted into the dorsal back musculature using a Floy tagging gun. JSATS cabled arrays were deployed at TDA and BON and autonomous node arrays were deployed near Celilo, Oregon (CR325); the BON forebay (CR236); the BON tailrace (CR233); near Knapp, Washington (CR156); and near Kalama, Washington (CR113) to monitor the kelts movement while passing through the dams and above mentioned river cross-sections.

Oxidized LDL (oxLDL) induces a pro-oxidative environment and promotes apoptosis, causing the progression of renal diseases in humans. Taurine is a semi-essential amino acid in mammals and has been shown to be a potent endogenous antioxidant. The kidney plays a pivotal role in maintaining the balance of taurine. However, the mechanisms underlying the protective effects of taurine against oxLDL-induced injury in renal epithelial cells have not been clarified. In the present study, we investigated the anti-apoptotic effects of taurine on human proximal tubular epithelial (HK-2) cells exposed to oxLDL and explored the related mechanisms. We observed that oxLDL increased the contents of ROS and of malondialdehyde (MDA), which is a lipid peroxidation by-product that acts as an indicator of the cellular oxidation status. In addition, oxLDL induced cell death and apoptosis in HK-2 cells. Pretreatment with taurine at 100 Î¼M significantly attenuated the oxLDL-induced cytotoxicity. We determined that oxLDL triggered the phosphorylation of ERK and, in turn, the activation of p53 and other apoptosis-related events, including calcium accumulation, destabilization of the mitochondrial permeability and disruption of the balance between pro-apoptotic Bax and anti-apoptotic Bcl-2 proteins. The malfunctions induced by oxLDL were effectively blocked by taurine. Thus, our results suggested that taurine exhibits potential therapeutic activity by preventing oxLDL-induced nephrotoxicity. The inhibition of oxLDL-induced epithelial apoptosis by taurine was at least partially due to its anti-oxidant activity and its ability to modulate the ERK and p53 apoptotic pathways. - Highlights: â¢ Oxidized LDL induced cytotoxicity and apoptosis in HK-2 cells. â¢ Pretreatment with taurine attenuated oxLDL-induced nephrotoxicity. â¢ Taurine protected against renal damages through inhibition of ROS generation. â¢ Taurine prevented apoptosis through modulation of the p53 phosphorylation.

H5PV2Mo10O40 polyoxometallate Keggin clusters supported on ZrO2, TiO2, SiO2, and Al2O3 are effective catalysts for CH3OH oxidation reactions to form HCHO, methyl formate (MF), and dimethoxymethane (DMM). Rates and selectivities and the structure of supported clusters depend on the surface properties of the oxide supports. Raman spectroscopy showed that Keggin structures remained essentially intact on ZrO2, TiO2, and SiO2 after treatment in air at 553 K, but decomposed to MoOx and VOx oligomers on Al2O3. Accessible protons per Keggin unit (KU) were measured during CH3OH oxidation by titration with 2,6-di-tert-butyl pyridine. For similar KU surface densities (0.28 0.37 KU/nm2), the number of accessible protons was larger on SiO2 than on ZrO2 and TiO2 and much smaller on Al2O3 supports, even though residual dimethyl ether (DME) synthesis rates after titrant saturation indicated that the fractional dispersion of KU was similar on the first three supports. These effects of support on structure and on H+ accessibility reflect varying extents of interaction between polyoxometallate clusters and supports. Rates of CH3OH oxidative dehydrogenation per KU were higher on ZrO2 and TiO2 than on SiO2 at similar KU surface densities (0.28 0.37 KU/nm2) and dispersion, indicating that redox properties of Keggin clusters depend on the identity of the support used to disperse them. ZrO2 and TiO2 supports appear to enhance the reducibility of anchored polyoxometallate clusters. Rates were much lower on Al2O3, because structural degradation led to less reactive MoOx and VOx domains. CH3OH reactions involve primary oxidation to form HCHO and subsequent secondary reactions to form DMM and MF. These reactions involve HCHO CH3OH acetalization steps leading to methoxymethanol (CH3OCH2OH) or hemiacetal intermediates, which condense with CH3OH on acid sites to form DMM or dehydrogenate to form MF. COx formation rates are much lower than those of other reactions, and DME forms in parallel

Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuOx) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu2O-like phase coexists with TiCuOx and TiOx domains. When the mixed-oxide surface is exposed at elevated temperatures (600â650 K) to oxygen, the formation of a well-ordered TiCuOx film occurs. Stepwise oxidation of TiCuOx shows that the formation of the mixed-oxide is faster than that of pure Cu2O. As the TimoreÂ Â» coverage increases, Ti-rich islands (TiOx) form. The adsorption of CO has been used to probe the exposed surface sites on the TiOxâCuOx system, indicating the existence of a new Cu+ adsorption site that is not present on Cu2O/Cu(111). Adsorption of CO on Cu+ sites of TiCuOx is thermally more stable than on Cu(111), Cu2O/Cu(111) or TiO2(110). The Cu+ sites in TiCuOx domains are stable under both reducing and oxidizing conditions whereas the Cu2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuOx films, which are not present on Cu(111), Cu2O/Cu(111), or TiO2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.Â«Â less

The thermodynamic laws governing the Otto and diesel cycle engines and the possible approaches that might be taken to increase the delivered efficiency of the reciprocating piston engine are discussed. The generic aspects of current research are discussed and typical links between research and the technical barriers to the engines' development are shown. The advanced engines are discussed individually. After a brief description of each engine and its advantages, the major technical barriers to their development are discussed. Also included for each engine is a discussion of examples of the linkages between these barriers and current combustion and thermodynamic research. For each engine a list of questions is presented that have yet to be resolved and could not be resolved within the scope of this study. These questions partially indicate the limit to the state of knowledge regarding efficiency characteristics of the advanced engine concepts. The major technical barriers to each of the engines and their ranges of efficiency improvement are summarized.

A parametric study of the liquid-phase fuel penetration of evaporating Diesel fuel jets has been conducted in a directinjection Diesel engine using laser elastic-scatter imaging. The experiments were conducted in an optically accessible Diesel engine of the ``heavy-duty`` size class at a representative medium speed (1200 rpm) operating condition. The density and temperature at TDC were varied systematically by adjusting the intake temperature and pressure. At all operating conditions the measurements show that initially the liquid fuel penetrates almost linearly with increasing crank angle until reaching a maximum length. Then, the liquid-fuel penetration length remains fairly constant although fuel injection continues. At a TDC density of 16.6 kg/m{sup 3} and a temperature of about 1000 K the maximum penetration length is approximately 23 mm. However, it varies significantly as TDC conditions are changed, with the liquid-length being less at higher temperatures and at higher densities. The corresponding apparent heat release rate plots are presented and the results of the liquid-phase fuel penetration are discussed with respect to the ignition delay and premixed bum fraction.

Within the framework of the ARTIST project of total fuel retreatment with ecological mixtures of solvents and extractants containing only C, H, O, and N atoms, a process segment of extraction of {sup 137}Cs from acidic stream was developed. The process with 25,27-Bis(1-octyloxy)calix[4]arene-crown- 6, DOC[4]C6, dissolved at its 0.01 M concentration in a mixture of 90 vol % 1-octanol and 10% dihexyl octanamide, DHOA was proposed as a viable variant due to its good multicycle performance, even with irradiated solvent, and due to the good chemical stability of the chosen combination of solvent mixture. (authors)

We report the first measurement of the opening angledistribution between pairs of jets produced in high-energy collisions oftransversely polarized protons. The measurement probes (Sivers)correlations between the transverse spin orientation of a proton and thetransverse momentum directions of its partons. With both beams polarized,the wide pseudorapidity (-1 leq eta leq +2) coverage for jets permitsseparation of Sivers functions for the valence and sea regions. Theresulting asymmetries are all consistent with zero and considerablysmaller than Sivers effects observed in semi-inclusive deep inelasticscattering (SIDIS). We discuss theoretical attempts to reconcile the newresults with the sizable transverse spin effects seen in SIDIS andforward hadron production in pp collisions.

The structural changes in the heme macrocycle and substituents caused by binding of Ca{sup 2+} to the diheme cytochrome c peroxidase from Paracoccuspantotrophus were clarified by resonance Raman spectroscopy of the inactive filly oxidized form of the enzyme. The changes in the macrocycle vibrational modes are consistent with a Ca{sup 2+}-dependent increase in the out-of-plane distortion of the low-potential heme, the proposed peroxidatic heme. Most of the increase in out-of-plane distortion occurs when the high affinity site I is occupied, but a small further increase in distortion occurs when site II is also occupied by Ca{sup 2+}or Mg{sup 2+}. This increase in the heme distortion also explains the red shift in the Soret absorption band that occurs upon Ca{sup 2+} binding. Changes also occur in the low frequency substituent modes of the heme, indicating that a structural change in the covalently attached fingerprint pentapeptide of the LP heme occurs upon CM{sup 2+} binding to site I. These structural changes, possibly enhanced in the semi-reduced form of the enzyme, may lead to loss of the sixth ligand at the peroxidatic heme and activation of the enzyme.

Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anion salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.

The peptides orexin-A and orexin-B and their G protein-coupled OX1 and OX2 receptors are involved in multiple physiological processes in the central nervous system and peripheral organs. Altered expression or signaling dysregulation of orexins and their receptors have been associated with a wide range of human diseases including narcolepsy, obesity, drug addiction, and cancer. Although orexin-A, its precursor molecule prepro-orexin and OX1 receptor have been detected in the human normal and hyperplastic prostate tissues, their expression and function in the prostate cancer (PCa) remains to be addressed. Here, we demonstrate for the first time the immunohistochemical localization of orexin-A in human PCa specimens, and the expression of prepro-orexin and OX1 receptor at both protein and mRNA levels in these tissues. Orexin-A administration to the human androgen-dependent prostate carcinoma cells LNCaP up-regulates OX1 receptor expression resulting in a decrease of cell survival. Noteworthy, nanomolar concentrations of the peptide counteract the testosterone-induced nuclear translocation of the androgen receptor in the cells: the orexin-A action is prevented by the addition of the OX1 receptor antagonist SB-408124 to the test system. These findings indicate that orexin-A/OX1 receptor interaction interferes with the activity of the androgen receptor which regulates PCa onset and progression, thus suggesting that orexin-A and its receptor might represent novel therapeutic targets to challenge this aggressive cancer. - Highlights: â¢ Orexin-A and OX1 receptor are present in human cancer prostate tissues. â¢ Orexin-A up-regulates OX1 receptor expression in LNCaP cells. â¢ Orexin-A inhibits testosterone-induced nuclear translocation of androgen receptor.

This paper was focused on core design, neutronics evaluation and fuel cycle analysis for Thorium-Uranium Breeding Recycle in current PWRs, without any major change to the fuel lattice and the core internals, but substituting the UOX pellet with Thorium-based pellet. The fuel cycle analysis indicates that Thorium-Uranium Breeding Recycle is technically feasible in current PWRs. A 4-loop, 193-assembly PWR core utilizing 17 x 17 fuel assemblies (FAs) was taken as the model core. Two mixed cores were investigated respectively loaded with mixed reactor grade Plutonium-Thorium (PuThOX) FAs and mixed reactor grade {sup 233}U-Thorium (U{sub 3}ThOX) FAs on the basis of reference full Uranium oxide (UOX) equilibrium-cycle core. The UOX/PuThOX mixed core consists of 121 UOX FAs and 72 PuThOX FAs. The reactor grade {sup 233}U extracted from burnt PuThOX fuel was used to fabrication of U{sub 3}ThOX for starting Thorium-. Uranium breeding recycle. In UOX/U{sub 3}ThOX mixed core, the well designed U{sub 3}ThOX FAs with 1.94 w/o fissile uranium (mainly {sup 233}U) were located on the periphery of core as a blanket region. U{sub 3}ThOX FAs remained in-core for 6 cycles with the discharged burnup achieving 28 GWD/tHM. Compared with initially loading, the fissile material inventory in U{sub 3}ThOX fuel has increased by 7% via 1-year cooling after discharge. 157 UOX fuel assemblies were located in the inner of UOX/U{sub 3}ThOX mixed core refueling with 64 FAs at each cycle. The designed UOX/PuThOX and UOX/U{sub 3}ThOX mixed core satisfied related nuclear design criteria. The full core performance analyses have shown that mixed core with PuThOX loading has similar impacts as MOX on several neutronic characteristic parameters, such as reduced differential boron worth, higher critical boron concentration, more negative moderator temperature coefficient, reduced control rod worth, reduced shutdown margin, etc.; while mixed core with U{sub 3}ThOX loading on the periphery of core has no

In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbenebis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(?4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(?4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(?4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(?4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(?-Cl)(?2-C8H14)2]2 (M = Rh, Ir) provide {?4-PhB(OxMe2)2ImMes?CH2}Rh(?-H)(?-Cl)Rh(?2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(?3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in CH bond oxidative addition providing the compounds {?4-PhB(OxMe2)2ImMes?CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex

Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

A multi-stage, isothermal, carbon monoxide preferential oxidation (PrOx) reactor comprising a plurality of serially arranged, catalyzed heat exchangers, each separated from the next by a mixing chamber for homogenizing the gases exiting one heat exchanger and entering the next. In a preferred embodiment, at least some of the air used in the PrOx reaction is injected directly into the mixing chamber between the catalyzed heat exchangers.

An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{ÎºÂ³-N,Si,C-PhB(OxMeÂ²)(OxMeÂ²SiHPh)ImMes}Rh(H)CO][HB(CâFâ )â] (2, OxMeÂ² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMeÂ²)âImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMeÂ²)âImMes}RhH(SiHPh)CO][HB(CâFâ )â] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmoreÂ Â» of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(CâFâ )â catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiHâ as the reducing agent.Â«Â less

A process is revealed for forming a 6-fluoro derivative of compounds in the L-Dopa family comprising the steps of protecting the groups attached to the benzene ring in the compound followed by serially reacting the protected compound with (a) iodine and silver trifluoroacetic acid; (b) Bb{sub 3}; (c) dit-butyldicarbonate; (d) hexamethyltin; (e) a fluoro compound; (f) hydrobromic acid; and (g) raising the pH to {<=}7. 1 fig.

A process for forming a 6-fluoro derivative of compounds in the L-Dopa family comprising the steps of protecting the groups attached to the benzene ring in the compound followed by serially reacting the protected compound with (a) iodine and silver trifluoroacetic acid; (b) Bb.sub.3 ; (c) dit-butyldicarbonate; (d) hexamethyltin; (e) a fluoro compound; (f) hydrobromic acid; and (g) raising the pH to .ltoreq.7.

In 1976, under section 4(e) of the Toxic Substances Control Act (TSCA), the US Congress created the TSCA Interagency Testing Committee (ITC) to decide which chemicals should be recommended to the Administrator of the US Environmental Protection Agency for testing. In 1988, under the Canadian Environmental Protection Act (CEPA), the Government of Canada created the Domestic Substances List and Priority Substances List. This paper briefly describes the ITC, the different ITC testing decisions and a few of the ITC`s 11,150 testing decisions for the 21,413 chemicals on the CEPA Domestic Substances List and some of the 24 testing decisions for the 44 chemicals and chemical groups on the CEPA.

A protected 6-trimethylstannyl dopa derivative has been synthesized for the as a precursor for the preparation of 6-[{sup 18}F]fluoro-L-dopa. The tin derivative readily reacts with electrophilic radiofluorinating agents such as [{sup 18}F]F{sub 2}, [{sup 18}F]OF{sub 2} and [{sup 18}F]AcOF. The [{sup 18}F]fluoro intermediate was easily hydrolyzed with HBr and the product 6-[{sup 18}F]fluoro-L-dopa was isolated after HPLC purification in a maximum radiochemical yield of 23%, ready for human use. 1 fig.

A protected 6-trimethylstannyl dopa derivative has been synthesized for the as a precursor for the preparation of 6-[.sup.18 F]fluoro-L-dopa. The tin derivative readily reacts with electrophilic radiofluorinating agents such as [.sup.18 F]F.sub.2, [.sup.18 F]OF.sub.2 and [.sup.18 F]AcOF. The [.sup.18 F]fluoro intermediate was easily hydrolyzed with HBr and the product 6-[.sup.18 F]fluoro-L-dopa was isolated after HPLC purification in a maximum radiochemical yield of 23%, ready for human use.

The top quark has been discovered in 1995 by CDF and D0 collaborations in proton-antiproton collisions at the Tevatron. The amount of data recorded by both experiments makes it possible to accurately measure the properties of this very massive quark. This thesis is devoted to the measurement of the top pair production cross-section via the strong interaction, in a final state composed of two electrons, two particle jets and missing transverse energy. It is based on a 1 fb{sup -1} data set collected by the D0 experiment between 2002 and 2006. The reconstruction and identification of electrons and jets is of major importance in this analysis, and have been studied in events where a Z boson is produced together with one or more jets. The Z+jets process is indeed the dominant physics background to top pair production in the dielectron final state. The primary goal of this cross-section measurement is to verify Standard Model predictions. In this document, this result is also interpreted to indirectly extract the top quark mass. Moreover, the cross-section measurement is sensitive to new physics such as the existence of a charged Higgs boson. The selection established for the cross-section analysis has been used to search for a H{sup +} boson lighter than the top quark, where the latter can decay into a W{sup +} or H{sup +} boson and a b quark. The model that has been studied makes the assumption that the H{sup +} boson can only decay into a tau lepton and a neutrino.

Measurements of the production cross section of W{sup +}W{sup -} pairs in p{bar p} collisions at 1.96 TeV and limits on trilinear gauge boson coupling (TGC) parameters are presented. The data were recorded with the CDF experiment at Tevatron during the 2001 and 2002 data taking periods in which a total integrated luminosity of 184 pb{sup -1} was collected. The data sample was filtered for events with two leptonic w boson decays where the charged leptons can be either electrons or muons. 17 events are observed against an expected background of 5.0{sub -0.8}{sup +2.2} events. The resulting cross-section is found to be {sigma}(p{bar p} {yields} W{sup +}W{sup -}) = 14.5{sub -5.1}{sup +5.8}(stat){sub -3.0}{sup +1.8}(syst) {+-} 0.9(lum) pb and agrees well with the Standard Model expectation. Limits on the TGC parameters {Delta}{kappa} and {lambda} are set under both the equal coupling scheme, that assumes the W boson couples identically to the Z and {gamma}, and the HISZ coupling scheme, that requires the couplings to respect SU(2){sub L} x &(1){sub Y} gauge symmetry. In both cases this is achieved by using a likelihood fit to the lepton-P{sub T} distribution of the 17 candidate events. The resulting limits are found to be: -0.4 < {Delta}{kappa} < +0.6({lambda} = 0); -0.3 < {lambda} < +0.4 ({Delta}{kappa} = 0) for the EQUAL couplings and -0.7 < {Delta}{kappa} < +0.9 ({lambda} = 0); -0.4 < {lambda} < +0.4 ({Delta}{kappa} = 0) for the HISZ couplings.

This report describes a 2008 acoustic telemetry survival study conducted by the Pacific Northwest National Laboratory for the Portland District of the U.S. Army Corps of Engineers. The study estimated the survival of juvenile Chinook salmon and steelhead passing Bonneville Dam (BON) and its spillway. Of particular interest was the relative survival of smolts detected passing through end spill bays 1-3 and 16-18, which had deep flow deflectors immediately downstream of spill gates, versus survival of smolts passing middle spill bays 4-15, which had shallow flow deflectors.

The complexation of Am(III) by oxalate has been investigated in solutions of NaClO{sub 4} up to 9.0 M ionic strength at 25{degrees}C. The dissociation constants of oxalic acid were determined by potentiometric titration, while the stability constants of the Am(III)-oxalate complexation were measured by the solvent extraction technique. A thermodynamic model was constructed to predict the apparent equilibrium constants at different ionic strengths by applying the Pitzer equation using parameters for the Na{sup +}-HOx{sup -}, Na{sup +}-Ox{sup -}, AmOx{sup +}-ClO{sub 4}{sup -}, and Na{sup +}-Am(Ox){sub 2}{sup -} interactions obtained by fitting the data.

A method of preparing a high temperature superconductor from an amorphous phase. The method involves preparing a starting material of a composition of Bi.sub.2 Sr.sub.2 Ca.sub.3 Cu.sub.4 Ox or Bi.sub.2 Sr.sub.2 Ca.sub.4 Cu.sub.5 Ox, forming an amorphous phase of the composition and heat treating the amorphous phase for particular time and temperature ranges to achieve a single phase high temperature superconductor.

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

Further reduction of the efficiency droop effect and further enhancements of internal quantum efficiency (IQE) and output intensity of a surface plasmon coupled, blue-emitting light-emitting diode (LED) by inserting a dielectric interlayer (DI) of a lower refractive index between p-GaN and surface Ag nanoparticles are demonstrated. The insertion of a DI leads to a blue shift of the localized surface plasmon (LSP) resonance spectrum and increases the LSP coupling strength at the quantum well emitting wavelength in the blue range. With SiO{sub 2} as the DI, a thinner DI leads to a stronger LSP coupling effect, when compared with the case of a thicker DI. By using GaZnO, which is a dielectric in the optical range and a good conductor under direct-current operation, as the DI, the LSP coupling results in the highest IQE, highest LED output intensity, and weakest droop effect.

Production rates for solvent extraction separation of the rare earths and yttrium from each other can be improved by the substitution of di(2-ethylhexyl) mono-thiophosphoric acid for di(2-ethylhexyl) phosphoric acid. The di(2-ethylhexyl) mono-thiophosphoric acid does not form an insoluble polymer at approximately 50% saturation as does the former extractant, permitting higher feed solution concentration and thus greater throughput.

HCCI and DI Engine Combustion | Department of Energy An Adaptive Multi-Grid Chemistry (AMC) Model for Efficient Simulation of HCCI and DI Engine Combustion An Adaptive Multi-Grid Chemistry (AMC) Model for Efficient Simulation of HCCI and DI Engine Combustion An adaptive multi-grid technique was used to group thermodynamically similar cells in order to reduce the calling frequency to the chemistry solver. deer08_shi.pdf (189.13 KB) More Documents & Publications Homogeneous Charge

Combustion Processes in a DI Diesel Engine | Department of Energy Combustion and Turbulence Models for the Simulation of Combustion Processes in a DI Diesel Engine Assessment of Combustion and Turbulence Models for the Simulation of Combustion Processes in a DI Diesel Engine Various applied combustion and turbulence models were investigated along with chemical kinetic mechanisms simulating a biodiesel-fueled engine deer09_ren.pdf (497.22 KB) More Documents & Publications Low Temperature

The report focu ses on the modification of the optical properties of ice crystals due to atmospheric black car bon (BC) contamination : the objective is to advance the predictive capabilities of climate models through an improved understanding of the radiative properties of compound particles . The shape of the ice crystal (as commonly found in cirrus clouds and cont rails) , the volume fraction of the BC inclusion , and its location inside the crystal are the three factors examined in this study. In the multiscale description of this problem, where a small absorbing inclusion modifies the optical properties of a much la rger non - absorbing particle, state - of - the - art discretization techniques are combined to provide the best compromise of flexibility and accuracy over a broad range of sizes .

The dissociation constants of oxalic acid (Ox), and the stability constants of Am3+, Cm3+ and Eu3+ with Ox2â have been determined at 25 Â°C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)n3 â 2n, where (M = Am3+, Cm3+ and Eu3+ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO4 concentration were used to estimate the Pitzer parameters for the respective interactions of Am3+, Cm3+ and Eu3+ with Ox.moreÂ Â» Furthermore, the stability constants data of Am3+ âOx measured in NaClO4 and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinideâoxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log Î²0101 = 6.30 Â± 0.06 and log Î²0102 = 10.84 Â± 0.06 for Am3+ was obtained by simultaneously fitting data in NaCl and NaClO4 media. Additionally, log Î²0101 = 6.72 Â± 0.08 and log Î²0102 = 11.05 Â± 0.09 for the Cm3+ and log Î²0101 = 6.67 Â± 0.08 and log Î²0102 = 11.15 Â± 0.09 for the Eu3+ were calculated by extrapolation of data to zero ionic strength in NaClO4 medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters Î²(0), Î²(1), and CÎ¦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent actinides and early lanthanides to ionic strength of 6.60 m in low temperature environments in the presence of Ox. Furthermore, the work is also applicable to the accurate modeling transport of rare earth elements in various environments under the surface conditions.Â«Â less

Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeOxTiOâ catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeOx and TiOâ. In these materials the interfaces between CeOx-TiOâ have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis and HR-STEM/STEM-EELS, to unravelmoreÂ Â» the local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeOx-TiOâ interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeOx loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiOâ support. The electronic structures of these catalysts indicate that the interaction between TiOâ and CeOâ is closely related to the local morphology of nanostructured CeOâ. CeÂ³âº cations were detected at the surface of CeOâ and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of HâO using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeOx-TiOâ catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the interface

Ultraviolet light absorbing compounds having two different chromophors in the same molecule, particularly the benzotriazole chromophor and either the dihydroxybenzophenone or dihydroxyacetophenone chromophor; specifically, the two compounds 3,5-[di(2H-benzotriazole-2-yl)]-2,4-dihydroxyacetophenone and 3,5-[di(2H-benzotriazole-2-yl)]2,4-dihydroxybenzophenone.

The high-nitrogen compound 3,6-di(azido)-1,2,4,5-tetrazine (DiAT) was synthesized by a relatively simple method and used as a precursor for the preparation of carbon nanospheres and nanopolygons, and nitrogen-rich carbon nitrides.

A composition and method for encapsulating a photovoltaic device which minimizes discoloration of the encapsulant. The composition includes an ethylene-vinyl acetate encapsulant, a curing agent, an optional ultraviolet light stabilizer, and/or an optional antioxidant. The curing agent is preferably 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; the ultraviolet light stabilizer is bis-(N-octyloxy-tetramethyl) piperidinyl sebacate and the antioxidant is selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite, tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and 2,2'-ethylidene bis(4,6-di-t-butylphenyl) fluorophosponite. The composition is applied to a solar cell then cured. The cured product contains a minimal concentration of curing-generated chromophores and resists UV-induced degradation.

The top quark is the heaviest standard model quark. Discovered in 1995 by the two Tevatron experiments it has atypical properties. In particular its time life is so short that it decays before hadronizing, so the top quark mass could be measured with a high precision. Data collected by the DÃ experiment between 2002 and 2009, which represent an integrated luminosity of 5.4 fbâ»Â¹, are used to measure the top quark mass by using the matrix element method in the three dilepton channels: dielectron, electron--muon and dimuon. The measured mass, 174.0 Â± 1.8 (stat.) Â± 2.4 (syst.) GeV, is in a good agreement with other measurements and limited by the systematic uncertainties for the first time in these channels. In this thesis different approaches have been studied to improve the accuracy of this measurement: the use of b-quark jet identification in order to optimize the selection of top--anti-top events and a better determination of the main systematic uncertainties. A special attention has been paid to the Monte-Carlo simulation of muons in DÃ: the improved smearing procedure for the simulated muons, discussed in this thesis, will be used to increase the accuracy of the top properties measurements as well as the precision of many other DÃ measurements.

This report summarizes work completed on DOE Contract DE-AC21-92MC28138, Development of a Natural Gas Systems Analysis Model (GSAM). The products developed under this project directly support the National Energy Technology Laboratory (NETL) in carrying out its natural gas R&D mission. The objective of this research effort has been to create a comprehensive, non-proprietary, microcomputer model of the North American natural gas market. GSAM has been developed to explicitly evaluate components of the natural gas system, including the entire in-place gas resource base, exploration and development technologies, extraction technology and performance parameters, transportation and storage factors, and end-use demand issues. The system has been fully tested and calibrated and has been used for multiple natural gas metrics analyses at NETL in which metric associated with NETL natural gas upstream R&D technologies and strategies under the direction of NETL has been evaluated. NETL's Natural Gas Strategic Plan requires that R&D activities be evaluated for their ability to provide adequate supplies of reasonably priced natural gas. GSAM provides the capability to assess potential and on-going R&D projects using a full fuel cycle, cost-benefit approach. This method yields realistic, market-based assessments of benefits and costs of alternative or related technology advances. GSAM is capable of estimating both technical and commercial successes, quantifying the potential benefits to the market, as well as to other related research. GSAM, therefore, represents an integration of research activities and a method for planning and prioritizing efforts to maximize benefits and minimize costs. Without an analytical tool like GSAM, NETL natural gas upstream R&D activities cannot be appropriately ranked or focused on the most important aspects of natural gas extraction efforts or utilization considerations.

The thermal conductivity of amorphous TaOx memristive films having variable oxygen content is measured using time domain thermoreflectance. Furthermore, the thermal transport is described by a two-partmodel where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. Additionally, the vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaOx switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically by field-induced chargemoreÂ Â» state migration.Â«Â less

The overall goal of this project was to design, evaluate, and engineer a Vanadium Red-Ox Flow Battery's integration into an existing wind site and micro-grid environment to determine if it is possible to achieve a fifteen percent reduction of diesel fuel usage during periods of peak load and otherwise stabilize the grid in potential high wind penetration systems. The bulk of the work was done by modeling the existing hybrid wind-diesel system and the proposed system with added flow battery storage. The flow battery was changed from a Vanadium Red-Ox to a Zinc Bromine flow battery by a different manufacturer during the modeling process. Several complications arose, but modeling proved to be successful and is ongoing. The development of a modeling platform for flow battery energy storage is a key element in evaluating both economic benefits and dispatch strategies for high penetration in micro-grid wind-diesel systems.

Computational Chemistry has revolutionized way of viewing molecules at the quantum mechanical scale by allowing simulating various chemical scenarios that are not possible to study in a laboratory. The remarkable applications of computational chemistry have promoted to design and test of the effectiveness of various methods for searching the conformational space of highly flexible molecules. In this context, we conducted a series of optimization and conformational searches on macrocyclic based ligands, 9N3Me5Ox, (1,4,7-tris(5-methyl-8-hydroxyquinoline)-1,4,7-triazacyclononane) and 12N3Me5Ox, (1,5,9-tris(5-methyl-8-hydroxyquinoline)-1,5,9-triazacyclododecane) and studied their selectivity and coordination behavior with some lanthanide metal ions in molecular mechanics and semiempirical methods. The methods include both systematic and random conformational searches for dihedral angles, torsion angles and Cartesian coordinates. Structural studies were carried out by using geometry optimization, coordination scans and electronic properties were evaluated. The results clearly show that chair-boat conformational isomer of 9N3Me5Ox ligand is more stable due to lower eclipsing ethane interaction and form stronger adduct complexes with lanthanide metal ion. This is because of the fact that, in a central unit of 9N3 of the ligand form six endo type bonds out of nine. The rest of bonds have trans conformation. In contrast, for the adduct of 12N3Me5Ox, two C-C bonds have on eclipsed conformation, and others have synclinal and antiperiplanar confirmations. The distortion of the two eclipsed conformations may affect the yields and the stability of the complexes.

Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. ThemoreÂ Â» thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(Î¼-Cl)]2 and [{BoMCptet}TiCl(Î¼-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.Â«Â less

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 Ã 2) relationship to the underlying TiO2(110)-(1 Ã 1). For the other half of the surface, it comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 Ã 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 Ã 1) areas,moreÂ Â» which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the waterâgas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. Finally, for Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3 + formed during WGS reaction conditions.Â«Â less

The Ag-CuOx system is being investigated as potential filler metals for use in air brazing high-temperature electrochemical devices such as solid oxide fuel cells and gas concentrators. The current study examines the effects of palladium addition on the high temperature joint strength of specimens prepared from yttria stabilized zirconia (YSZ) bars brazed with the binary Ag-CuOx, and 15Pd-Ag-CuO. It was found that while the binary Ag-CuOx system exhibits stronger room temperature strength than the 15Pd system the strength is reduced to values equivalent of the 15Pd system at 800°C. The 15Pd system exhibits a lower ambient temperature strength that is retained at 800°C. In both systems the failure mechanism at high temperature appears to be peeling of the noble metal component from the oxide phases and tearing through the noble metal phase whereas sufficient adhesion is retained at lower temperatures to cause fracture of the YSZ substrate.

In this study, a new synthetic route for the formation of titanium oxydifluoride (TiOF2) through the process of direct fluorination via a fluidized bed reactor system and the associated electrochemical properties of the powders formed from this approach are reported. The flexibility of this synthetic route was demonstrated using precursor powders of titanium dioxide (TiO2) nanoparticles, as well as a reduced TiOxNy. An advantage of this synthetic method is the ability to directly control the extent of fluorination as a function of reaction temperature and time. The reversible capacity of TiOF2 anodes was found to depend greatly upon the precursormoreÂ Â» employed. The TiOF2 synthesized from TiO2 and TiOxNy showed reversible capacities of 300 mAh g-1 and 440 mAh g-1, respectively, over 100 cycles. The higher reversible capacity of the TiOF2 powders derived from TiOxNy likely relate to the partial reduction of the Ti in the fluorinated electrode material, highlighting a route to optimize the properties of conversion electrode materials.Â«Â less

We introduce an extended version of oxDNA, a coarse-grained model of deoxyribonucleic acid (DNA) designed to capture the thermodynamic, structural, and mechanical properties of single- and double-stranded DNA. By including explicit major and minor grooves and by slightly modifying the coaxial stacking and backbone-backbone interactions, we improve the ability of the model to treat large (kilobase-pair) structures, such as DNA origami, which are sensitive to these geometric features. Further, we extend the model, which was previously parameterised to just one salt concentration ([Na{sup +}] = 0.5M), so that it can be used for a range of salt concentrations including those corresponding to physiological conditions. Finally, we use new experimental data to parameterise the oxDNA potential so that consecutive adenine bases stack with a different strength to consecutive thymine bases, a feature which allows a more accurate treatment of systems where the flexibility of single-stranded regions is important. We illustrate the new possibilities opened up by the updated model, oxDNA2, by presenting results from simulations of the structure of large DNA objects and by using the model to investigate some salt-dependent properties of DNA.

In this study, the high thermochemical stability of CO2 makes it very difficult to achieve the catalytic conversion of the molecule into alcohols or other hydrocarbon compounds, which can be used as fuels or the starting point for the generation of fine chemicals. Pure metals and bimetallic systems used for the CO2 â CH3OH conversion usually bind CO2 too weakly and, thus, show low catalytic activity. Here, we discuss a series of recent studies that illustrate the advantages of metalâoxide and metalâcarbide interfaces when aiming at the conversion of CO2 into methanol. CeOx/Cu(111), Cu/CeOx/TiO2(110), and Au/CeOx/TiO2(110) exhibit an activity formoreÂ Â» the CO2 â CH3OH conversion that is 2â3 orders of magnitude higher than that of a benchmark Cu(111) catalyst. In the Cuâceria and Auâceria interfaces, the multifunctional combination of metal and oxide centers leads to complementary chemical properties that open active reaction pathways for methanol synthesis. Efficient catalysts are also generated after depositing Cu and Au on TiC(001). In these cases, strong metalâsupport interactions modify the electronic properties of the admetals and make them active for the binding of CO2 and its subsequent transformation into CH3OH at the metalâcarbide interfaces.Â«Â less

A mixed extractant solvent that includes at least one dialkyloxycalix[4]arenebenzocrown-6 compound, 4',4',(5')-di-(t-butyldicyclohexano)-18-crown-6, at least one modifier, and, optionally, a diluent. The dialkyloxycalix[4]arenebenzocrown-6 compound is 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(decyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(dodecyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. The modifier is a primary alcohol. A method of separating cesium and strontium from an aqueous feed is also disclosed, as are dialkyloxycalix[4]arenebenzocrown-6 compounds and an alcohol modifier.

Coplanar polychlorinated biphenyls (PCBs) may facilitate development of atherosclerosis by stimulating pro-inflammatory pathways in the vascular endothelium. Nutrition, including fish oil-derived long-chain omega-3 fatty acids, such as docosahexaenoic acid (DHA, 22:6{omega}-3), can reduce inflammation and thus the risk of atherosclerosis. We tested the hypothesis that cyclopentenone metabolites produced by oxidation of DHA can protect against PCB-induced endothelial cell dysfunction. Oxidized DHA (oxDHA) was prepared by incubation of the fatty acid with the free radical generator 2,2-azo-bis(2-amidinopropane) dihydrochloride (AAPH). Cellular pretreatment with oxDHA prevented production of superoxide induced by PCB77, and subsequent activation of nuclear factor-{kappa}B (NF-{kappa}B). A{sub 4}/J{sub 4}-neuroprostanes (NPs) were identified and quantitated using HPLC ESI tandem mass spectrometry. Levels of these NPs were markedly increased after DHA oxidation with AAPH. The protective actions of oxDHA were reversed by treatment with sodium borohydride (NaBH{sub 4}), which concurrently abrogated A{sub 4}/J{sub 4}-NP formation. Up-regulation of monocyte chemoattractant protein-1 (MCP-1) by PCB77 was markedly reduced by oxDHA, but not by un-oxidized DHA. These protective effects were proportional to the abundance of A{sub 4}/J{sub 4} NPs in the oxidized DHA sample. Treatment of cells with oxidized eicosapentaenoic acid (EPA, 20:5{omega}-3) also reduced MCP-1 expression, but less than oxDHA. Treatment with DHA-derived cyclopentenones also increased DNA binding of NF-E2-related factor-2 (Nrf2) and downstream expression of NAD(P)H:quinone oxidoreductase (NQO1), similarly to the Nrf-2 activator sulforaphane. Furthermore, sulforaphane prevented PCB77-induced MCP-1 expression, suggesting that activation of Nrf-2 mediates the observed protection against PCB77 toxicity. Our data implicate A{sub 4}/J{sub 4}-NPs as mediators of omega-3 fatty acid-mediated protection against the

Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, an Fe/SSZ-13 catalyst active in NH3-SCR was synthesized. MÃ¶ssbauer and FTIR spectroscopies were used to probe the nature of the Fe sites. In the fresh sample, the majority of Fe species are extra-framework cations. The likely monomeric and dimeric ferric ions in hydrated form are [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+, based on MÃ¶ssbauer measurements. During the severe hydrothermal aging (HTA) applied in this study, a majority of cationic Fe species convert to FeAlOx and clustered FeOx species, accompanied by severe dealumination of the SSZ-13 framework. The clustered FeOx species do not give a sextet MÃ¶ssbauer spectrum, indicating that these are highly disordered. However, some Fe species in cationic positions remain after aging as determined from MÃ¶ssbauer measurements and CO/NO FTIR titrations. NO/NH3 oxidation reaction tests reveal that dehydrated cationic Fe are substantially more active in catalyzing oxidation reactions than the hydrated ones. For NH3-SCR, enhancement of NO oxidation under âdryâ conditions promotes SCR rates below ~300 â¢ C. This is due mainly to contribution from the âfastâ SCR channel. Above ~300 â¢ C, enhancement of NH3 oxidation under âdryâ conditions, however, becomes detrimental to NOx conversions. The HTA sample loses much of the SCR activity below ~300 â¢ C; however, above ~400 â¢ C much of the activity remains. This may suggest that the FeAlOx and FeOx species become active at such elevated temperatures. Alternatively, the high-temperature activity may be maintained by the remaining extra-framework cationic species. For potential practical applications, Fe/SSZ-13 may be used as a co-catalyst for Cu/CHA as integral aftertreatment SCR catalysts on the basis of the stable high temperature activity after hydrothermal aging. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy

Hemoglobin adducts have been used as biomarkers of exposure to reactive chemicals. Glycidol, an animal carcinogen, has been reported to form N-(2,3-dihydroxy-propyl)valine adducts to hemoglobin (diHOPrVal). To support the use of these adducts as markers of glycidol exposure, we investigated the kinetics of diHOPrVal formation and its elimination in vitro and in vivo. Five groups of rats were orally administered a single dose of glycidol ranging from 0 to 75 mg/kg bw, and diHOPrVal levels were measured 24 h after administration. A dose-dependent increase in diHOPrVal levels was observed with high linearity (R{sup 2} = 0.943). Blood sampling at different time points (1, 10, 20, or 40 days) from four groups administered glycidol at 12 mg/kg bw suggested a linear decrease in diHOPrVal levels compatible with the normal turnover of rat erythrocytes (life span, 61 days), with the calculated first-order elimination rate constant (k{sub el}) indicating that the diHOPrVal adduct was chemically stable. Then, we measured the second-order rate constant (k{sub val}) for the reaction of glycidol with N-terminal valine in rat and human hemoglobin in in vitro experiments with whole blood. The k{sub val} was 6.7 Â± 1.1 and 5.6 Â± 1.3 (pmol/g globin per Î¼Mh) in rat and human blood, respectively, indicating no species differences. In vivo doses estimated from k{sub val} and diHOPrVal levels were in agreement with the area under the (concentrationâtime) curve values determined in our earlier toxicokinetic study in rats. Our results indicate that diHOPrVal is a useful biomarker for quantification of glycidol exposure and for risk assessment. - Highlight: â¢ Glycidol-hemoglobin adduct (diHOPrVal) was characterized for exposure evaluation. â¢ We studied the kinetics of diHOPrVal formation and elimination in vitro and in vivo. â¢ Dose dependent formation and chemical stability were confirmed in the rat study. â¢ In vivo dose (AUC) of glycidol could be estimated from diHOPrVal levels

The paper compares hydrographic and terrain categories in the geospatial data standards of the US, Taiwan, and Russian Federation where the dominant languages used are from di erent language families. It aims to identify structural and semantic di erences between similar categories across three geospatial data standards. By formalizing the data standard structures and identifying the properties that di erentiate sibling categories in each geospatial data standard using well-known formal relations and quality universals, we develop a common basis on which hydrographic and terrain categories in the three data standards can be compared. The result suggests that all three data standards structure categories with a mixture of relations with di erent meaning even though most of them are well-known relations in top-level ontologies. Similar categories can be found across all three standards but exact match between similar categories are rare.

Process for the production of 5'-deoxy-5-fluorouridine and the corresponding /sup 18/F compound by the reaction of fluorine or acetyl hypofluorite with 2', 3'-di-O-acetyl-5'-deoxyuridine followed by hydrolysis.

Alumni > The Energy Materials Center at Cornell Raymond Burns Product Research Technologist - Exxon Mobile raymond.burns@gmail.com Formerly a member of the DiSalvo Group, Ray earned his PhD in August 2013

An application of alkyne metathesis to 1,2-di(prop-1-ynyl)arenes, producing dehydrobenzannulenes, is described. An efficient method for selective Sonogashira couplings of bromoiodoarenes under conditions of microwave irradiation is also reported.

16, 2008 Visiting Speaker Program - July 16, 2008 The Visiting Speaker Program event with presentations on the effectiveness of collaboration within the federal government and current and future challenges facing agencies and the entire country. Assistant Secretary James Rispoli introduced Mr. Frank DiGiammarino and Mr. Jonathan Breul and made opening remarks at the program. Mr. DiGiammarino, NAPA Vice President of Strategic Initiatives, presented the topic of collaboration and its impacts on

This invention relates to novel ultraviolet light absorbers having two chromophors in the same molecule, and more particularly to benzotriazole substituted dihydroxybenzophenones and acetophenones. More particularly, this invention relates to 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxybenzophenone and 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxyacetophenone which are particularly useful as an ultraviolet light absorbers.

Insensitive explosive compositions were prepared by reacting di-isocyanate and/or poly-isocyanate monomers with an explosive diamine monomer. Prior to a final cure, the compositions are extrudable. The di-isocyanate monomers tend to produce tough, rubbery materials while polyfunctional monomers (i.e. having more than two isocyanate groups) tend to form rigid products. The extrudable form of the composition may be used in a variety of applications including rock fracturing.

9 Columbia River Corridor The Columbia River Corridor projects selected for Recovery A t f di i l d d li hi f iliti di ti Act funding include demolishing facilities, remediating waste sites, and containing and treating contamination in groundwater. The projects support completing cleanup along the Columbia River and shrinking the active area of cleanup to the center of the Hanford Site (the Central Plateau) by 2015 1 of the Hanford Site (the Central Plateau) by 2015. May 2009 Shrinking the

A waveguide having a non-conductive material with a high permeability (.mu., .mu..sub.r for relative permeability) and/or a high permittivity (.di-elect cons., .di-elect cons..sub.r for relative permittivity) positioned within a housing. When compared to a hollow waveguide, the waveguide of this invention, reduces waveguide dimensions by .varies..mu. ##EQU00001## The waveguide of this invention further includes ridges which further reduce the size and increases the usable frequency bandwidth.

Insensitive explosive compositions were prepared by reacting di-isocyanate and/or poly-isocyanate monomers with an explosive diamine monomer. Prior to a final cure, the compositions are extrudable. The di-isocyanate monomers tend to produce tough, rubbery materials while polyfunctional monomers (i.e. having more than two isocyanate groups) tend to form rigid products. The extrudable form of the composition may be used in a variety of applications including rock fracturing.

representation of production. Tag loss and mortality is monitored, and the tagging files are then uploaded to the regional PTAGIS database. The PIT tags are read as the fish pass through the coils of the detector. For detection of smolts, there are detectors installed at six Snake and Columbia River dams, including Lower Granite (LGR), Little Goose (LGS), Lower Monumental (LMN), McNary (MCN), John Day (JDA), and Bonneville (BON). These site abbreviations will be used throughout this document. For detection of returning adults, there is current detection capability at LGR, and starting in migration year 2002, PIT tagged adults will be detected at both BON and MCN.

The dissociation constants of oxalic acid (Ox), and the stability constants of Am3+, Cm3+ and Eu3+ with Ox2â have been determined at 25 Â°C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)n3 â 2n, where (M = Am3+, Cm3+ and Eu3+ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO4 concentration were used to estimate the Pitzer parameters for the respective interactions of Am3+, Cm3+ and Eu3+ with Ox. Furthermore, the stability constants data of Am3+ âOx measured in NaClO4 and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinideâoxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log Î²0101 = 6.30 Â± 0.06 and log Î²0102 = 10.84 Â± 0.06 for Am3+ was obtained by simultaneously fitting data in NaCl and NaClO4 media. Additionally, log Î²0101 = 6.72 Â± 0.08 and log Î²0102 = 11.05 Â± 0.09 for the Cm3+ and log Î²0101 = 6.67 Â± 0.08 and log Î²0102 = 11.15 Â± 0.09 for the Eu3+ were calculated by extrapolation of data to zero ionic strength in NaClO4 medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters Î²(0), Î²(1), and CÎ¦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent

Organic soil amendments can ameliorate metal toxicity to plants by redistributing metals to less available fractions. The objective of this study was to determine the effects of organic amendments on Zn distribution among soil fractions. Two soils were amended with five organic waste materials (some of which contained Zn) or commercial humic acid with and without 400 mg kg{sup {minus}1} Zn, incubated, and fractionated using a sequential extraction technique. Where no Zn was added most of the metals were in the residual fraction. Commercial compost, poultry litter, and industrial sewage sludge increased Zn in the exchangeable (EXC), organic (OM), and manganese oxide (MnOx) fractions due to Zn in the materials. Spent mushroom compost (SMC) redistributed Zn from the EXC fraction to the MnOx fraction for the coarse-textured soil. Where Zn was added, most of the metal was in the EXC and OM fractions. The SMC and humic acid lowered Zn in the EXC fraction and increased Zn in the other fractions. Effects of the organic materials on Zn in soil fractions were more evident for the sandy soil dominated by quartz in the clay than for the finer-textured soil dominated by kaolinite in the clay-size fraction. It was concluded that organic materials high in Zn can increase Zn in the EXC, OM, and MnOx fractions where the soil is not contaminated and others such as SMC and HA can lower the potential availability of Zn in contaminated soils by redistributing it from the EXC to less soluble fractions.

Nanostructured RuOx/TiO2(110) catalysts have a remarkable catalytic activity for CO oxidation at temperatures in the range of 350â375 K. Furthermore, the RuO2(110) surface has no activity. The state-of-the-art DFT calculations indicate that the main reasons for such an impressive improvement in the catalytic activity are: (i) a decrease of the diffusion barrier of adsorbed O atoms by around 40%, from 1.07 eV in RuO2(110) to 0.66 eV in RuOx/TiO2(110), which explains the shift of the activity to lower temperatures and (ii) a lowering of the barrier by 20% for the association of adsorbed CO and O species to give CO2moreÂ Â» (the main barrier for the CO oxidation reaction) passing from around 0.7 eV in RuO2(110) to 0.55 eV in RuOx/TiO2(110). We show that the catalytic properties of ruthenia are strongly modified when supported as nanostructures on titania, attaining higher activity at temperatures 100 K lower than that needed for pure ruthenia. As in other systems consisting of ceria nanostructures supported on titania, nanostructured ruthenia shows strongly modified properties compared to the pure oxide, consolidating the fact that the nanostructuring of oxides is a main way to attain higher catalytic activity at lower temperatures.Â«Â less

ABSTRACT. The supported (Rh2-yCryO3)/GaN photocatalyst was examined as a model nitride photocatalyst system to assist in the development of fundamental structure photoactivity relationships for UV activated water splitting. Surface characterization of the outermost surface layers by High Sensitivity-LEIS and High Resolution-XPS revealed for the first time that the GaN support consists of a GaOx outermost surface layer and a thin film of GaOxNy in the surface region. HR-XPS also demonstrates that the supported (Rh2-yCryO3) mixed oxide nanoparticles (NPs) exclusively consist of Cr+3 and Rh+3 cations and are surface enriched for the supported (Rh2-yCryO3)/GaN photocatalyst. Bulk analysis by Raman and UV-vis spectroscopy show that the bulk molecular and electronic structures, respectively, of the GaN support are not perturbed by the deposition of the (Rh2-yCryO3) mixed oxide NPs. The function of the GaN bulk lattice is to generate photoexcited electrons/holes, with the electrons harnessed by the surface Rh+3 sites for evolution of H2 and the holes trapped at the Ga oxide/oxynitride surface sites for splitting of water and evolving O2. These new structure-photoactivity relationships for supported (Rh2-yCryO3)/GaN also extend to the best performing visible light activated supported (Rh2-yCryO3)/(Ga1-xZnx)(N1-xOx) photocatalyst.

Cu- and Fe/SSZ-13 catalysts with the same Cu(Fe)/Al ratios are synthesized using the same parent SSZ-13 starting material. The catalytic performance for both fresh and hydrothermally aged catalysts is tested with NO and NH3 oxidation, and standard SCR reactions under steady-state conditions, and standard and fast SCR under temperature-programmed conditions. For standard SCR, Cu/SSZ-13 shows much better low-temperature performance which can be explained by NH3-inhibition of Fe/SSZ-13. During hydrothermal aging, both catalysts undergo dealumination but Fe/SSZ-13 dealuminates more severely. For aged catalysts, Cu/SSZ-13 gains oxidation activities due to formation of CuOx. However, Fe/SSZ-13 loses oxidation activities although formation of FeOx clusters and FeAlOx species also occur. Because of such physical properties differences, aged Cu/SSZ-13 loses while Fe/SSZ-13 maintains high-temperature SCR selectivities. A physical mixture of aged catalysts provides stable SCR performance in a wide temperature range and is able to decrease N2O formation at high reaction temperatures. This suggests that Fe/SSZ-13 can be used as a cocatalyst for Cu/SSZ-13 for transportation applications. During temperature-programmed SCR reactions, weak hysteresis is found during standard SCR due to NH3 inhibition. For fast SCR, hysteresis caused by NH4NO3 inhibition is much more significant. NH4NO3 deposition is greatly enhanced by BrÃ¸nsted and Lewis acidity of the catalysts.

An improved high vacuum microwave window has been developed that utilizes high density polyethylene coated on two sides with SiOx, SiNx, or a combination of the two. The resultant low dielectric and low loss tangent window creates a low outgassing, low permeation seal through which broad band, high power microwave energy may be passed. No matching device is necessary and the sealing technique is simple. The features of the window are broad band transmission, ultra-high vacuum compatibility with a simple sealing technique, low voltage standing wave ratio, high power transmission and low cost.

An improved high vacuum microwave window has been developed that utilizes high density polyethylene coated on two sides with SiOx, SiNx, or a combination of the two. The resultant low dielectric and low loss tangent window creates a low outgassing, low permeation seal through which broad band, high power microwave energy may be passed. No matching device is necessary and the sealing technique is simple. The features of the window are broad band transmission, ultra-high vacuum compatibility with a simple sealing technique, low voltage standing wave ratio, high power transmission and low cost. 5 figs.

I|ex~ ~ ILKE&y~~~ *ORNL/RASA-92/14 OAK RIDGE NATIONAL LABORATORY Results of the Radiological Survey at the former Alba Craft Laboratory Site *z riiiriri-lrirfZ Properties, Oxford, Ohio (OX001) M. E. Murray K. S. Brown R. A. Mathis MANAGED BY MARTIN MARIETTA ENERGY SYSTEMS, INC. FOR THE UNITED STATES DEPARTMENT OF ENERGY | ~~DEPARTMENT OF ENERGY This report has been reproduced directly from the best available copy. Available to DOE and DOE contractors from the Office of Scientific and Techni-

Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. The thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(Î¼-Cl)]2 and [{BoMCptet}TiCl(Î¼-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.

CONTRACTOR AND ADDRESS COEPPRACT FOR: TERM: COMMT.SSION OBLIGATION PAYMENT TO m MADE BY: CONTRACT NO. AT(30-l)-1247 CONTRACT pl AMERICAN MACHINE Ah'D FOUNDRY COMP'N' Second Avenue and 56th Street Brooklyn, New York MA$HR\?No AND OTHER WORK AND SERVICES August o' 19% to December 31 9 0 'lyj! 512O,ox).OO Division of Disbursement, United States Treasury Department,' New York, New York. Subn-it invoices to: United States Atomic Energy Corrcni&ion, P. 0. %x 30, Ansonia Station New York 23, l!tw

Highlights:  Dioctanoyl-PC (diC8PC) supported growth of a yeast mutant defective in PC synthesis.  diC8PC was converted to PC species containing longer acyl residues in the mutant.  Both acyl residues of diC8PC were replaced by longer fatty acids in vitro.  This system will contribute to the elucidation of the acyl chain remodeling of PC. - Abstract: A yeast strain, in which endogenous phosphatidylcholine (PC) synthesis is controllable, was constructed by the replacement of the promoter of PCT1, encoding CTP:phosphocholine cytidylyltransferase, with GAL1 promoter in a double deletion mutant of PEM1 and PEM2, encoding phosphatidylethanolamine methyltransferase and phospholipid methyltransferase, respectively. This mutant did not grow in the glucose-containing medium, but the addition of dioctanoyl-phosphatidylcholine (diC8PC) supported its growth. Analyses of the metabolism of {sup 13}C-labeled diC8PC ((methyl-{sup 13}C){sub 3}-diC8PC) in this strain using electrospray ionization tandem mass spectrometry revealed that it was converted to PC species containing acyl residues of 16 or 18 carbons at both sn-1 and sn-2 positions. In addition, both acyl residues of (methyl-{sup 13}C){sub 3}-diC8PC were replaced with 16:1 acyl chains in the in vitro reaction using the yeast cell extract in the presence of palmitoleoyl-CoA. These results indicate that PC containing short acyl residues was remodeled to those with acyl chains of physiological length in yeast.

The Portland District of the U.S. Army Corps of Engineers contracted with the Pacific Northwest National Laboratory (PNNL) to conduct three studies using acoustic telemetry to estimate detection probabilities and survival of juvenile Chinook salmon at three hydropower projects on the lower Columbia River. The primary goals were to estimate detection and survival probabilities based on sampling with JSATS equipment, assess the feasibility of using JSATS for survival studies, and estimate sample sizes needed to obtain a desired level of precision in future studies. The 2006 JSATS arrays usually performed as well or better than radio telemetry arrays in the JDA and TDA tailwaters, and underperformed radio arrays in the BON tailwater, particularly in spring. Most of the probabilities of detection on at least one of all arrays in a tailwater exceeded 80% for each method, which was sufficient to provide confidence in survival estimates. The probability of detection on one of three arrays includes survival and detection probabilities because fish may die or pass all three arrays undetected but alive.

The authors analyze alternative fuel-powerstrain options for internal combustion engine automobiles. Fuel/engine efficiency, energy use, pollutant discharges, and greenhouse gas emissions are estimated for spark and compression ignited, direct injected (DI), and indirect injected (II) engines fueled by conventional and reformulated gasoline, reformulated diesel, compressed natural gas (CNG), and alcohols. Since comparisons of fuels and technologies in dissimilar vehicles are misleading, the authors hold emissions level, range, vehicle size class, and style constant. At present, CNG vehicles have the best exhaust emissions performance while DI diesels have the worst. Compared to a conventional gasoline fueled II automobile, greenhouse gases could be reduced by 40% by a DI CNG automobile and by 25% by a DI diesel. Gasoline- and diesel-fueled automobiles are able to attain long ranges with little weight or fuel economy penalty. CNG vehicles have the highest penalty for increasing range, due to their heavy fuel storage systems, but are the most attractive for a 160-km range. DI engines, particularly diesels, may not be able to meet strict emissions standards, at least not without lowering efficiency.

Interfacial magnetoelectric coupling (MEC) is a viable path to achieve electrical writing of magnetic information in spintronic devices. For the prototypical Fe/BaTiO3 (BTO) system, only tiny changes of the interfacial Fe magnetic moment upon reversal of the BTO dielectric polarization have been predicted so far. Here, by using X-ray magnetic circular dichroism in combination with high resolution electron microscopy and first principles calculations, we report on an undisclosed physical mechanism for interfacial MEC in the Fe/BTO system. At the Fe/BTO interface, an ultrathin FeOx layer exists, whose magnetization can be electrically and reversibly switched on-off at room-temperature by reversing themoreÂ Â» BTO polarization. The suppression / recovery of interfacial ferromagnetism results from the asymmetric effect that ionic displacements in BTO produces on the exchange coupling constants in the adjacent FeOx layer. The observed giant magnetoelectric response holds potential for optimizing interfacial MEC in view of efficient, low-power spintronic devices.Â«Â less

Realizing the commercialization of high-performance and robust perovskite solar cells urgently requires the development of economically scalable processing techniques. Here we report a high-throughput ultrasonic spray-coating (USC) process capable of fabricating perovskite film-based solar cells on glass substrates with power conversion efficiency (PCE) as high as 13.04%. Perovskite films with high uniformity, crystallinity, and surface coverage are obtained in a single step. Moreover, we report USC processing on TiOx/ITO-coated polyethylene terephthalate (PET) substrates to realize flexible perovskite solar cells with PCE as high as 8.02% that are robust under mechanical stress. In this case, an optical curing technique was used to achieve a highly-conductive TiOx layer on flexible PET substrates for the first time. The high device performance and reliability obtained by this combination of USC processing with optical curing appears very promising for roll-to-roll manufacturing of high-efficiency, flexible perovskite solar cells.

Mono-metallic nickel and rhodium catalysts and bimetallic Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}, CeZrO{sub 2} and CeMgOx were prepared and evaluated for catalyzing the steam and autothermal reforming of n-butane. The binary Ni-Rh supported on La-Al{sub 2}O{sub 3} catalysts with low weight loading of rhodium exhibited higher H{sub 2} yields than Ni or Rh alone. The Ni-Rh/CeZrO{sub 2} catalyst exhibited higher performance and no coke formation, compared to the same metals on other supports. A NiAl{sub 2}O{sub 4} spinel phase was obtained on all Ni and Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}. The presence of rhodium stabilized the spinel phase as well as NiOx species upon reforming while Ni alone was mostly reduced into metallic species. Extended X-ray absorption fine-structure analysis showed evidence of Ni-Rh alloy during preparation and even further after an accelerated aging at 900C in a H{sub 2}/H{sub 2}O atmosphere.

Highlights: â¢ SiNWs modified with Pd, Au and Pt were used as photocatalysts to degrade MB. â¢ Yield of photodegardation increases with UV irradiation time. â¢ SiNWs modified with Pd nanoparticles show the best photocatalytic activity. â¢ A degradation of 97% was obtained after 200 min of UV irradiation. - Abstract: Silicon nanowires (SiNWs) modified with Au, Pt and Pd nanoparticles were used as heterogeneous photocatalysts for the photodegradation of methylene blue in water under UV light irradiation. The modification of SiNWs was carried out by deposition of metal nanoparticles using the electroless metal deposition (EMD) technique. The effect of metal nanoparticles deposition time on the photocatalytic activity was studied. It was found that the photocatalytic activity of modified SiNWs was enhanced when the deposition time of metal nanoparticles was increased. In addition of modified SiNWs with Pt, Au and Pd nanoparticles, oxidized silicon substrate (Ox-Si), oxidized silicon nanowires (Ox-SiNWs) and hydrogen-terminated silicon nanowires (H-SiNWs) were also evaluated for the photodegradation of methylene blue.

Lectin-like oxidized LDL receptor-1 (LOX-1) is an oxidized LDL receptor, and its role in restenosis after angioplasty remains unknown. We used a balloon-injury model of rabbit aorta, and reverse transcription-polymerase chain reaction revealed that LOX-1 mRNA expression was modest in the non-injured aorta, reached a peak level 2 days after injury, and remained elevated until 24 weeks after injury. Immunohistochemistry and in situ hybridization showed that LOX-1 was not detected in the media of non-injured aorta but expressed in both medial and neointimal smooth muscle cells (SMC) at 2 and 24 weeks after injury. Low concentrations of ox-LDL (10 {mu}g/mL) stimulated the cultured SMC proliferation, which was inhibited by antisense oligonucleotides of LOX-1 mRNA. Double immunofluorescense staining showed the colocalization of LOX-1 and proliferating cell nuclear antigen in human restenotic lesion. These results suggest that LOX-1 mediates ox-LDL-induced SMC proliferation and plays a role in neointimal formation after vascular injury.

Polyclic aromatic hydrocarbons, also called Graphene Molecules (GMs), with chemical composition C132H36(COOH)2 were synthesized in-situ on the surface of transparent nanocrystaline indium tin oxide (nc-ITO) electrodes. Their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared here these were foundmoreÂ Â» to be E1,ox 0 = 0.77Â± 0.01 V and E2,ox 0 = 1.24 Â± 0.02 V vs. NHE for the first and second oxidation and E1,red 0 = -1.50 Â± 0.04 V for the first reduction. The charge transfer processes are found to be non-ideal. The non-ideality factors associated with the oxidation and reduction processes suggest presence of strong interactions between the GM redox centers. Under the conditions of potential cycling GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.Â«Â less

A CuOx-CeOx/Al2O3 catalyst was studied with in-situ transmission Cu K XAS for the total oxidation of propane as model reaction for the catalytic elimination of volatile organic compounds. The local Cu structure was determined for the catalyst as such, after pre-oxidation and after reduction with propane. The catalyst as such has a local CuO structure. No structural effect was observed upon heating in He up to 600 deg. C or after pre-oxidation at 150 deg. C. A full reduction of the Cu2+ towards metallic Cu0 occurred, when propane was fed to the catalyst. The change in local Cu structure during propane reduction was followed with a time resolution of 1 min. The {chi}(k) scans appeared as linear combinations of start and end spectra, CuO and Cu structure, respectively. However, careful examination of the XANES edge spectra indicates the presence of a small amount of additional Cu1+ species.

Polyclic aromatic hydrocarbons, also called Graphene Molecules (GMs), with chemical composition C132H36(COOH)2 were synthesized in-situ on the surface of transparent nanocrystaline indium tin oxide (nc-ITO) electrodes. Their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared here these were found to be E1,ox0 = 0.77± 0.01 V and E2,ox 0 = 1.24 ± 0.02 V vs. NHE for the first and second oxidation and E1,red0 = -1.50 ± 0.04 V for the first reduction. The charge transfer processes are found to be non-ideal. The non-ideality factors associated with the oxidation and reduction processes suggest presence of strong interactions between the GM redox centers. Under the conditions of potential cycling GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.

In order to realize an efficient ECRH and also to reduce stray radiation due to non-absorbed power during ECRH, it is necessary to excite a wave that is absorbed well near the electron cyclotron resonance. In the normal fusion magnetic field confinement machine and in the electron cyclotron frequency range, WKB approximation is valid almost all the way from antenna to the absorption region due to the large scale-length of the plasma density Î»{sub n} and the magnetic shear Ï{sub s} as compared with the local wavelength Î»{sub 0}. In these situation, it is well known that the O/X mode propagates as O/X mode if Ï{sub s} â« Î»{sub 0}. Even in these situation, if Ï{sub s} and Î»{sub n} are comparable and |1/Î»{sub O}â1/Î»{sub X}|Ï{sub s} âª 1, there still remains the question from where âXâ - or âOâ - mode become âXâ - or âOâ mode at the peripheral region. In order to simulate this situation, one dimensional full wave calculation code which solve electromagnetic wave equation under arbitrary magnetic field configuration and arbitrary density profile for a given polarization state are developed and incorporated in the upgraded ray tracing code LHDGauss. It is tried to find the density and shear scale lengths region where the mode mixing effect is not negligible.

Highlights:  Nickel nanostructure-encapsulated bacteria were prepared using electroless deposition.  Bacterium surface was activated by red-ox reaction of its surface amino acids.  Interfacial changes at cell surfaces were investigated using fluorescence spectroscopy.  TEM and AFM depicted morphological changes.  Antibacterial activity of nanostructure was examined against different bacteria strains. - Abstract: Nickel nanostructure-encapsulated bacteria were prepared using the electroless deposition procedure and activation of bacterium cell surface by red-ox reaction of surface amino acids. The electroless deposition step occurred in the presence of Ni(II) and dimethyl amine boran (DMAB). Interfacial changes at bacteria cell surfaces during the coating process were investigated using fluorescence spectroscopy. Fluorescence of tryptophan residues was completely quenched after the deposition of nickel onto bacteria surfaces. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) depicted morphological changes on the surface of the bacterium. It was found that the Ni coated nanostructure was mechanically stable after ultrasonication for 20 min. Significant increase in surface roughness of bacteria was also observed after deposition of Ni clusters. The amount of coated Ni on the bacteria surface was calculated as 36% w/w. The antibacterial activity of fabricated nanostructure in culture media was examined against three different bacteria strains; Escherichia coli, Bacillus subtilis and Xantomonas campestris. The minimum inhibitory concentrations (MIC) were determined as 500 mg/L, 350 mg/L and 200 mg/L against bacteria, respectively.

An improved method is presented for producing normorphine from morphine. Morphine as the starting material is acetylated by treatment with acetylating agents to produce di-acetyl morphine (heroin). The acetylated compound is reacted with cyanating agents to produce di-acetyl-cyanonormorphine (cyanonorheroin). The di-acetyl-cyanonormorphine compound is then treated in accordance with the improved hydrolysis reactions of the present invention in which concentrated hydrochloric acid is employed for a limited time period to hydrolyze the acetyl group therefrom forming cyanonormorphine. Subsequently, the reaction mixture is diluted and hydrolysis of the cyano groups from the cyanonormorphine is effected with a longer contact time with dilute hydrochloric acid thereby producing normorphine. A high over-all conversion and production of a high purity product which may be radioactlvely labeled, if desired, is obtained by operation of the process.